Method for the preparation of a polyester block copolymer, a polyester block copolymer composition and method for the preparation thereof

ABSTRACT

The present invention I relates to a method for the preparation of a polyester block copolymer (P1) characterized in that in the method for the preparation of 100% by weight of the polyester block copolymer (P1) by allowing to react A% by weight of a crystalline aromatic polyester with B% by weight of lactones (A+B=100), (B+0.5)% by weight of lactones are added into A% by weight of a crystalline aromatic polyester, and not less than 0.5% by weight of unreacted lactones are remained with respect to 100% by weight of the polyester block copolymer (P1) after reaction.  
     The present invention II relates to a method for the preparation of a polyester block copolymer (P′1) having a high molecular weight characterized in that the polyester block copolymer (P1) is allowed to further react in a solid phase.  
     The present invention III relates to a polyester block copolymer composition (R) obtained by thermally-processing a polyester block copolymer composition (Q) obtained by melt-mixing 100 parts by weight of a polyester block copolymer (P) with 0.1-5 parts by weight of an epoxy compound (C) having one or more epoxy groups under an inert gas atmosphere and not less than 120° C. in a solid phase, and further, at a temperature lower than a melting point of the polyester block copolymer composition (R).  
     The present invention IV relates to a polyester block copolymer composition which comprises thermally-kneading 0.5-5.0 parts by weight of a mono or more functional epoxy compound (C) and 0.01-3.0 parts by weight of a complex-formable agent for a metal (G) such as an oxalic acid derivative and a salicylic acid derivative or a hydrazide derivative with 100 parts by weight of a polyester block copolymer (P1) obtained by a reaction of a crystalline aromatic polyester (A1) with lactones (B).  
     The present invention V relates to a polyester block copolymer composition which comprises, in obtaining the polyester block copolymer composition by allowing to react the crystalline aromatic polyester (A1) with lactones (B), adding and thermally-kneading 0.5-5.0 parts by weight of an epoxy compound (C) having one or more pieces of epoxy groups (including at least 0.2 part by weight of two or more functional epoxy compound) and, optionally, 0-2.0 parts by weight of a carbodiimide compound (E) to 100 parts by weight of a polyester block copolymer (P3) obtained by allowing to react 0.1-100% by mol of at least one of a multifunctional compound (D) having at least three pieces of at least one kind of carboxylic group (i), hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A1).  
     The present invention VI relates to a polyester block copolymer composition which comprises, in obtaining said polyester block copolymer composition by allowing to react the crystalline aromatic polyester (A1) with lactones (B), adding and thermally-kneading 0.1-5.0 parts by weight of an epoxy compound (C) having one or more pieces of epoxy groups and 0-2.0 parts by weight of a carbodiimide compound (E) to 100 parts by weight of a polyester block copolymer (P3) obtained by allowing to react 0.1-200% by mol of at least one of an aliphatic or aromatic multifunctional compound (D) having at least three pieces of carboxylic group hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A1).  
     The present invention VII relates to a polyester block copolymer composition (R) which comprises, in obtaining the polyester block copolymer composition by allowing to react the crystalline aromatic polyester (A1) with lactones (B), heating a polyester block copolymer composition (Q) at a solid phase, and the composition (Q) is obtained by adding and thermally-kneading 0.1-5.0 parts by weight of at least one kind of an epoxy compound (C) having one or more pieces of epoxy groups to 100 parts by weight of a polyester block copolymer (P) obtained by allowing to react 0.1-200% by mol of at least one of a multifunctional compound (D) having at least three pieces of carboxylic group (i), hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A1).

TECHNICAL FIELD

[0001] The present invention No. I relates to an efficient method forthe preparation of a polyester block copolymer which is excellent inheat resistance and hydrolysis resistance, in which lactones areaddition-polymerized onto a crystalline aromatic polyester.

[0002] The present invention No. II relates to a method for thepreparation of a polyester block copolymer which is excellent in heatresistance and hydrolysis resistance, and which has a higher molecularweight, in which the polyester block copolymer obtained in the presentinvention No. I is further allowed to react in a solid state.

[0003] The present invention No. III relates to a polyester blockcopolymer composition which is excellent in heat resistance andhydrolysis resistance, color hue, and melt viscosity stability, and amethod for the preparation thereof.

[0004] The present invention No. IV relates to a polyester blockcopolymer composition which is excellent in heat resistance under acontact with a metal and a polyvinyl chloride (PVC), and relates to aheat-sensitive body for a heater cable in which polyester blockcopolymer-based resin is employed.

[0005] The present invention Nos. V and VI relate to a polyester blockcopolymer composition which is excellent in a blow-moldability and heatresistance.

[0006] The present invention No. VII relates to a polyester blockcopolymer composition composed of a crystalline aromatic polyester andlactones, and relates to a method for the preparation thereof, and whichis excellent in a blow-moldability and heat resistance.

BACKGROUND TECHNOLOGY

[0007] Prior arts in relation to the present invention Nos. I and II areas follows.

[0008] Many polyester block copolymers possesses a mechanical propertysuch as flexibility, and widely enlarge uses such as parts for cars andelectric and electronic parts as a thermoplastic elastomer which isexcellent in heat resistance and chemical resistance, which contains acrystalline aromatic polyester unit such as a polybutylene terephthalateunit as a hard segment, and in which crystallinity is lowered bycombination of a long chain diol with an aromatic dicarboxylic acid inspite of an aliphatic polyether such as a poly(alkyleneoxide) glycol,and/or an aliphatic polyester such as a polylactone and/or a polyester,and an aromatic polyester.

[0009] Hitherto, as a technology for giving flexibility to a crystallinearomatic polyester, JP-B-73004116 Official Gazette states a method forobtaining a block copolymer having a elasticity by reaction of acrystalline aromatic polyester with lactones. The method stated hereinis a first method which shows that a block copolymer can be obtained byan addition reaction of lactones, however, there is nothing described inrelation to an importance of residual unreacted lactone monomers afterthe above-described reaction and a technical effect, and there is alsonothing described in relation to a melting point in the block copolymerobtained.

[0010] On the other hand, JP-B-77049037 Official Gazette describes amethod for polymerizing lactones under the presence of a crystallinearomatic polyester which is in a solid phase. By descriptions, it isshown that a method in which a reaction is conducted in a melting statehas a problem of a remarkable decline in a melting point of thecrystalline aromatic polyester, and it can be solved by conducting areaction under a solid condition.

[0011] However, it includes a problem that since it is a reaction at alow temperature, there is required a long time of period in thereaction, and since productivity is worse, and it lacks practicability.

[0012] Further, JP-B-96009661, JP-B-93023289, JP-B-93023290,JP-B-95033434, JP-B-94033435, JP-A-05043666, and JP-A-05043667 OfficialGazettes all describe a method for allowing to continuously react acrystalline aromatic polyester with lactones, and some of the Gazettesinclude descriptions including a step for removing unreacted lactones.Removal of the unreacted lactone described herein has an effect forreducing a monomer smell in the polyester block copolymer and, moreover,by conducting a continuous removal operation, it has an effect forfurther reducing concentration of the unreacted lactones in thepolyester block copolymer.

[0013] Still further, some of the above-described prior arts describethat there is included a step for conducting a polycondensation reactionin a solid state, and the polycondensation reaction in a solid state hasan effect for increasing a solution viscosity of a polyester blockcopolymer (P1).

[0014] However, all of the prior arts only describe that a thermalproperty such as a melting point of a resin obtained are decided by rawmaterials to be employed, reaction temperature, reaction time of period,and conditions for removing unreacted lactones, and all the prior artsdo not describe a technical concept and a specific method forintentionally improving the thermal property by increasing the amount ofthe lactones to be introduced and by remaining the amount of theunreacted lactones.

[0015] In JP-A-02252729 and JP-A-04072325 Official Gazettes, there isdescribed a method for elevating a melting point of a block copolymerobtained. The JP-A-02252729 Official Gazette describes a method in whichthere are dissolved a crystalline aromatic polyester and lactones at alower temperature, and those have an effect for reducing decompositionreaction by heating, however, there is small an effect for preventing adecline of a melting point, further, occasionally, a reaction time ofperiod unpreferably becomes long. Further, the JP-A-04072325 OfficialGazette describes that the lactones is partially added in advance in ahighly-polymerized state, and elevation of a melting point can beeffectively actualized. However, in spite of an inherent low cost in thelactones, the method partially highly-polymerized in advance includes aproblem of a fair adverse affection to total profitability.

[0016] JP-A-61287922 Official Gazette describes that in a method for thepreparation of an elastic polyester by allowing to react a crystallinearomatic polyester with lactones, the method for the preparation of anelastic polyester characterized in that an addition polymerization isconducted by continuously feeding a melted crystalline polyester andlactones into a reaction vessel, and then, those are allowed to reactwith each other in a solid state.

[0017] However, even in the method, there are not shown a technicalconcept and a specific method, etc., that thermal properties areintentionally elevated by increasing the amount of the lactones and byremaining the amount of unreacted lactones.

[0018] As described hereinabove, those have been still insufficient as amethod for the preparation of a polyester block copolymer having a highmelting point and a high molecular weight.

[0019] Prior arts in relation to the present invention No. III are asfollows.

[0020] However, in relation to the polyester block copolymer composed ofa hard segment and a soft segment described in the prior arts for thepresent invention No. I, an industrially-produced polymer is notsufficient in heat resistance and hydrolysis resistance, and, in thecase that it is applied to a melting molding method such as a blowmolding and extrusion molding in which a high melt viscosity isrequired, there has been caused a problem that moldability is worse.

[0021] Accordingly, as a method for elevating a heat resistance andhydrolysis resistance in a polyester block copolymer, there have beenproposed a variety of methods until now. Further, there are proposedmethods simultaneously elevating a melt viscosity in the many proposes.For example, JP-B-77030999 and the above-described JP-B-77049037Official Gazettes propose a method for increasing a melt viscosity by asolid phase polymerization. However, in the method for increasing a meltviscosity proposed herein, there is required a very long time of periodfor heating and, further, hydrolysis resistance is not improved at all.

[0022] JP-B-91077826 Official Gazette proposes a method for melt-mixinga monofunctional epoxy compound with a bifunctional epoxy compound. Bythe method, although heat resistance and hydrolysis resistance areelevated, the hydrolysis resistance is not sufficient, an elevation of amelt viscosity is also insufficient.

[0023] In order to allow to become sufficient the hydrolysis resistanceof the polyester elastomer obtained by the method, it is required thatan excessive amount of the epoxy compounds are added, resulting in thata melting point lowers, and viscosity change is large in reheating, andit is problematic in molding stability in the case of conducting a moreprecise molding process.

[0024] JP-B-92021703, JP-B-89052441, and JP-B-86042930 Official Gazettesdescribe the further addition of a metal salt of a carboxylic acid as anaccelerator in a reaction.

[0025] However, melt viscosity in resins obtained herein is not stillsufficient and, it is anxious that such the addition of the metal saltsunpreferably affects to hydrolysis resistance, and it preferably causesto lower a color hue. On the other hand, as a method for improving amelt viscosity stability, JP-B-88031491 Official Gazette proposes amethod of addition of an epoxy compound and carboxylic acids. In themethod, since there are added the carboxylic acids which changehydrolysis resistance to worse, there must be added a large amount ofthe epoxy compounds in order to obtain a sufficient hydrolysisresistance, resulting in that there are caused a cost increase andcrystallinity lowers.

[0026] Prior arts in relation to the present invention No. IV are asfollows.

[0027] In recent years, there have been employed composite materials ofsynthetic resins with metals and PVC in many fields including electriccables. The composite materials are molded by an extrusion moldingmethod or a fusing method, and employed in a variety of uses.

[0028] As a use of such the materials, there is a heater cable for anelectric blanket and an electric carpet in which heat resistance isrequired.

[0029] Structure of the heater cable, as shown in FIG. 1, is composed ofa center wire 1, a short wire 2, a heating wire 3, a heat-sensitive body4, and an outer cover 5. The heat-sensitive body 4 has a function as afuse.

[0030] This functions in order to cut a heater circuit by fusing theheat-sensitive body 4 which fuses at a narrow temperature range whentemperature abnormally elevates, and there have been mainly employed anylon 12 and a nylon 11 until now. Further, a heat-resistible polyesteris employed as the center wire 1, PVC is employed as the outer cover 5,and copper and a copper alloy are employed as the short wire 2 and theheater wire 3.

[0031] The heater wire composed of the composite materials are oftenexposed to heat cycles in view of functions thereof and, if theheat-sensitive body 4 is poor in heat resistance, even though exothermfrom the heater wire 3 is in a normal range, the heater circuit isoccasionally cut or, contrarily, a fusing function does not occasionallywork even in the case of abnormal temperature elevation, resulting inthat fire accident is occasionally caused.

[0032] Heretofore, there have been mainly employed resins such as thenylon 12 and the nylon 11 as the heat-sensitive body 4.

[0033] As the resins, although there is employed a resin which isexcellent in heat resistance and does not contain an additive, or aresin composition in which a hindered phenol-based stabilizer is mixedto prevent heat deterioration, those include many problems.

[0034] Prior arts in relation to the present invention Nos. V, VI, andVII are as follows.

[0035] As a method for preparing a polyester block copolymer by allowingto react an aromatic polyester with lactones, there have been known amethod (JP-A-48004116 Official Gazette) by allowing to react acrystalline aromatic polyester with a lactone, a method (JP-A-48004115Official Gazette) by allowing to react a crystalline aromatic polyesterwith a lactone and to chain-extend by allowing to react an initialcopolymer with a multifunctional acylating agent, and a method (theabove-described JP-B-77049037 Official Gazette) for polymerizing thelactones in a solid phase under the presence of a crystalline aromaticpolyester.

[0036] Although the polyester block copolymers obtained by the methodshave excellent rubbery elasticity and excellent weatherability, thecopolymers are insufficient in heat resistance, and include a drawbackthat viscosity, extension, and strength remarkably lower by exposing toa high temperature for a long time of period.

[0037] Further, the copolymers do not have a strain-hardening propertywhich is an important property in blow-molding, and there cannot beobtained a molded article having uniform thickness.

[0038] Therefore, in order to improve heat resistance and moldability ofthe above-described polyester-type block copolymers, there have beenproposed a method (JP-A-58162654 Official Gazette) in which a mono ormore functional epoxy compound is mixed, a method (JP-A-59152947Official Gazette) in which there are formulated a mono or morefunctional epoxy compound and a metal salt of an aliphatic carboxylicacid, and a method (JP-A-59155458 Official Gazette) in which there areformulated a mono or more functional epoxy compound and anethylene-carboxylic acid copolymer. However, melt viscosity isrelatively low in the compositions obtained in the methods.

[0039] There have been problems that because it is difficult to obtain amutual relationship between a dependence of a melt viscosity uponextension speed and a mixing amount of the metal salt of an aliphaticcarboxylic acid, and quality cannot be stabilized, and heat resistancelowers, etc.

[0040] Recently, as a method for solving all the problems, althoughthere has been proposed a method (JP-A-07331046 Official Gazette) inwhich there are formulated two or more functional epoxy compounds and animidazole compound, a dependence of a melt viscosity upon extensionspeed (It is called a strain-hardening property, that is, it is acharacteristic of viscosity increase with an increase of an extendingspeed. Accordingly, a larger hardening property prevents an excessiveextension of an extended portion in blow molding owing to a largerviscosity, and an unextended portion is extended owing to a lowerviscosity, as a result, uniform thickness is obtained.) is stillinsufficient. and there cannot be obtained a molded article havinguniform thickness in blow molding and, further, there has been a problemthat discoloration is remarkable.

DISCLOSURE OF THE INVENTION

[0041] Purpose of the present invention No. I is to provide a method forthe preparation of a polyester block copolymer from a crystallinearomatic polyester and, specifically, to provide a method for thepreparation of a polyester block copolymer which has a low crystallinityand a high melting viscosity and which is excellent in heat resistance,processability, and hydrolysis resistance.

[0042] The present inventors, as a result of an investigation of amethod for the preparation of a polyester block copolymer which isexcellent in heat resistance, processability, hydrolysis resistance, anda high melt viscosity, found out that in the method for the preparationof a polyester block copolymer (P1) by allowing to react a crystallinearomatic polyester (A1) with lactones, thermal characteristics of thepolyester block copolymer (P1) can be improved by controlling anintroducing amount of lactones (B) with respect to the above-describedcrystalline aromatic polyester (A1) and an amount of unreacted lactonesremained in the polyester block copolymer (P1), and the presentinvention No. I has been completed.

[0043] Purpose of the present invention No. II is to provide a methodfor the preparation of a high molecular weight polyester block copolymerfrom a crystalline aromatic polyester and, specifically, to provide amethod for the preparation of a polyester block copolymer which is lowin crystallinity, and which is excellent in heat resistance,processability, hydrolysis resistance, and which has a high meltviscosity and a higher molecular weight.

[0044] The present inventors, as a result of an investigation of amethod for the preparation of a polyester block copolymer in whichcrystallinity is lowered in a crystalline aromatic polyester, and whichis excellent in heat resistance, processability, hydrolysis resistance,and which has a high melt viscosity, found out that in the method forthe preparation of a polyester block copolymer (P1) by allowing to reactthe crystalline aromatic polyester with lactones, thermalcharacteristics of the polyester block copolymer (P1) can be improved bycontrolling an introducing amount of unreacted lactones remained in thepolyester block copolymer (P1) obtained by the reaction and a polyesterblock copolymer (P′1) obtained through a reaction in a solid phase canbe more highly-polymerized, and the present invention No. II has beencompleted.

[0045] Purpose of the present invention No. III is to provide apolyester block copolymer composition and a method for the preparationthereof, which is excellent in heat resistance, hydrolysis resistanceand color hue, and which has a high melt viscosity and melt viscositystability, and which is appropriate in molding processing.

[0046] The present inventors, as a result of an intensive investigationfor obtaining a resin composition which is excellent in heat resistanceand hydrolysis resistance and a polyester block-based copolymer whichhas a high melt viscosity and a melt viscosity stability and which isappropriate in molding processability, have found that theabove-described problems can be solved by heating under a specifiedcondition after mixing a mono or more functional epoxy compound with thepolyester block copolymer, and the present invention No. III has beencompleted.

[0047] Purpose of the present invention No. IV is to solve a problemthat thermal deterioration is accelerated and heat resistance becomesinsufficient by a combined action of a produced copper ion with acovered PVC or hydrochloric acid isolated from the covered PVC becausethe above-described heater cable is exposed to heat cycles andtemperature elevates to approximately 100° C. or so, and theheat-sensitive body such as a nylon 12 and nylon 11 is brought intocontact with copper or a copper alloy which is a short wire or a heatingwire, and those are brought into contact with a PVC cover at a clearancebetween wound short wires.

[0048] The present inventors, as a result of an intensive investigationfor solving the problems in the prior arts, have found out that apolyester block copolymer composition is not apt to be suffered by acombined thermal deterioration even under a circumstance in which it isbrought into contact with a metal such as copper and copper alloy andPVC, the composition is excellent in heat resistance and hydrolysisresistance, the composition is obtained by allowing to react a polyestercopolymer with an epoxy compound after mixing a polyester blockcopolymer with a specified epoxy compound and a metal complex andheating and kneading, and the present invention No. IV has beencompleted.

[0049] Purpose of the present invention Nos. V, VI, and VII is toprovide a polyester block copolymer composition which has an excellentmoldability, excellent heat resistance, and rubbery elasticity, andwhich can be applied to a variety of molding such as blow moldingwithout any problems.

[0050] The present inventors, as a result of an intensive investigation,have found out that a polyester block copolymer composition can solvethe above-described problems by an elevated strain-hardening property,and the present invention Nos. V and VI have been completed. Thepolyester block copolymer composition is obtained by mixing a polyesterblock copolymer with an epoxy compound, and then, heating and kneading.The polyester block copolymer is obtained by copolymerizing throughadding a multifunctional compound having three or more carboxylic groupsor hydroxyl groups while allowing to react a crystalline aromaticpolyester with lactones.

[0051] The present inventors have found out that a polyester blockcopolymer composition can solve the above-described problems by anelevated strain-hardening property, and the present invention No. VIIhave been completed. The polyester block copolymer composition isobtained by adding an epoxy compound to a polyester block copolymer andheating in a solid phase. The polyester block copolymer is obtained byadding a specified amount of an aliphatic or aromatic multifunctionalcompound having a specified multifunctional group while allowing toreact a crystalline aromatic polyester with lactones.

[0052] That is, the present invention No. 1 relates to a method for thepreparation of a polyester block copolymer (P1) characterized in that inthe method for the preparation of 100% by weight of the polyester blockcopolymer (P1) by allowing to react A% by weight of a crystallinearomatic polyester (A1) with B% by weight of lactones (B) (proviso thatA+B=100), not less than (B+0.5)% by weight of lactones (B) areintroduced into A% by weight of a crystalline aromatic polyester (A1),and not less than 0.5% by weight of unreacted lactones are remained withrespect to 100% by weight of the polyester block copolymer (P1) afterpreparation of the copolymer.

[0053] The present invention No. 2 relates to a method for thepreparation of a polyester block copolymer (P1) as described in thepresent invention No. 1, in which not less than (B+2.5)% by weight ofthe lactones (B) are introduced and not less than 2.5% by weight ofunreacted lactones are remained with respect to 100% by weight of thepolyester block copolymer (P1) after preparation of the copolymer.

[0054] The present invention No. 3 relates to a method for thepreparation of a polyester block copolymer (P1) as described in thepresent invention No. 1 or 2, in which reaction proportion (A)/(B) ofthe crystalline aromatic polyester (A1) with respect to the lactones (B)is 95/5-20/80.

[0055] The present invention No. 4 relates to a method for thepreparation of a polyester block copolymer (P1) as described in any oneof the present invention Nos. 1-3, in which the unreacted lactones areremoved from the polyester block copolymer (P1) after reaction.

[0056] The present invention No. 5 relates to a method for thepreparation of a polyester block copolymer (P1) as described in any oneof the present invention Nos. 1-4, in which the unreacted lactones arecontinuously removed.

[0057] The present invention No. 6 relates to a method for thepreparation of a polyester block copolymer (P1) as described in any oneof the present invention Nos. 1-5, in which the crystalline aromaticpolyester (A1) and the lactones (B) are continuously supplied into areaction vessel and allowed to addition-polymerize, and the polyesterblock copolymer (P1) is continuously taken out.

[0058] The present invention No. 7 relates to a method for thepreparation of a polyester block copolymer (P1) as described in any oneof the present invention Nos. 1-6, in which the crystalline aromaticpolyester (A1) is a polybutylene terephthalate.

[0059] The present invention No. 8 relates to a method for thepreparation of a polyester block copolymer (P1) as described in any oneof the present invention Nos. 1-7, in which the lactones (B) arecaprolactone.

[0060] The present invention No. 9 relates to a method for thepreparation of a polyester block copolymer (P′1) having a high molecularweight characterized in that after having prepared the polyester blockcopolymer (P1) as described in any one of the present invention Nos.1-8, it is further allowed to react in a solid phase.

[0061] The present invention No. 10 relates to a method for thepreparation of a polyester block copolymer (P′1) having a high molecularweight as described in the present invention No 9, in which reaction ina solid phase is continuously conducted.

[0062] The present invention No. 11 relates to a polyester blockcopolymer composition (R) obtained by thermally-processing a polyesterblock copolymer composition (Q) obtained by melt-mixing 100 parts byweight of a polyester block copolymer (P) with 0.1-5 parts by weight ofan epoxy compound (C) having one or more epoxy groups under an inert gasatmosphere and not less than 120° C. in a solid phase, and further, at atemperature lower than a melting point of the polyester block copolymercomposition (R) obtained.

[0063] The present invention No. 12 relates to a polyester blockcopolymer composition (R) as described in the present invention No. 11,characterized in that the polyester block copolymer (P) is a polyesterblock copolymer (P1) obtained by allowing to react a crystallinearomatic polyester (A1) with lactones (B).

[0064] The present invention No. 13 relates to a polyester blockcopolymer composition (R) as described in the present invention No. 11,characterized in that the polyester block copolymer (P) is a polyesterblock copolymer (P2) obtained by a polycondensation and/or ring-openingpolymerization of monomer components constructing a crystalline aromaticpolyester (A1); monomer components constructing a low crystallinepolyester (A4); an aliphatic polyether (A2); and/or polylactone (A3).

[0065] The present invention No. 14 relates to a polyester blockcopolymer composition (R) as described in any one of the presentinvention Nos. 11-13, characterized in that the epoxy compound (C) is anepoxy compound (C2) having two or more epoxy groups.

[0066] The present invention No. 15 relates to a polyester blockcopolymer composition (R) as described in any one of the presentinvention Nos. 11-14 which is obtained by thermally-processing thepolyester block copolymer composition (Q) at not less than 150° C. and,moreover, at a temperature of 100- to 5° C.-lower than a melting pointof the polyester block copolymer composition (R).

[0067] The present invention No. 16 relates to a polyester blockcopolymer composition (R) as described in any one of the presentinvention Nos. 11-15 which is obtained by further thermally-processingthe polyester block copolymer composition (Q) after preheating at atemperature less than a melting point of the polyester block copolymercomposition (R) and, moreover, at a temperature of not more than 150° C.

[0068] The present invention No. 17 relates to a polyester blockcopolymer composition (R) as described in any one of the presentinvention Nos. 11-16 in which there are formulated at least one kind ofcompounds selected from the group consisting of a hindered phenol-basedcompound, a sulphur-based compound, a phosphorus-based compound, aphenyl amine-based compound, and a hindered amine-based compound.

[0069] The present invention No. 18 relates to a polyester blockcopolymer composition (R) as described in any one of the presentinvention Nos. 11-17, in which an acid value is not more than 0.5mgKOH/g in the polyester block copolymer composition (R) and, moreover,a melting point (Tm(R)) of the composition (R) is not less than a 10°C.-lower temperature than a melting point (Tm(P)) of the polyester blockcopolymer (P) which is a raw material.

[0070] Tm(P)−10° C.≦Tm(R)

[0071] The present invention No. 19 relates to a polyester blockcopolymer composition (R) as described in any one of the presentinvention Nos. 11-18, in which a melt viscosity stability (MI(T, P,t+10)/(MI(T, P, t)) is 0.5-2.0 in the polyester block copolymercomposition (R).

[0072] In the formula, the melt index (MI(T, P, t)) value is a valuemeasured at a heating temperature (T), loading (P), and heating time ofperiod (t) based on a method described in JIS K7210. Herein, T is atemperature higher than a 5° C.-higher temperature than a melting pointof the composition (R) and, it is a minimum temperature of experimentaltemperatures described in Table 1 of the JIS K7210, and P is a valueselected as ranging in 1-30 g/10 minutes in the MI value. The MI(T, P,t+10) is a value in which the heating time of period is t+10 minutes inconditions of the T and P.

[0073] The present invention No. 20 relates to a method for thepreparation of a polyester block copolymer composition (R) characterizedin that there is thermally-treated a polyester block copolymercomposition (Q) in which 100 parts by weight of a polyester blockcopolymer (P) is thermally mixed with 0.1-5 parts by weight of an epoxycompound (C) having at least one epoxy groups under an inert gasatmosphere and at not less than 120° C. in a solid phase and atemperature less than a melting point of the obtained polyester blockcopolymer composition (R).

[0074] The present invention No. 21 relates to a polyester blockcopolymer composition which comprises thermally-mixing 100 parts byweight of a polyester block copolymer (P1) obtained by a reaction of acrystalline aromatic polyester (A1) and lactones (B) with 0.5-5.0 partsby weight of a mono or more functional epoxy compound (C) and 0.01-3.0parts by weight of a complex-formable agent for a metal (G).

[0075] The present invention No. 22 relates to a polyester blockcopolymer composition as described in the present invention No. 21,characterized in that the crystalline aromatic polyester (A1) is apolyester of an aromatic dicarboxylic acid which is an essential acidcomponent (a) and an aliphatic dicarboxylic acid and/or a cycloaliphaticdicarboxylic acid which are optionally added with an aliphatic diol, anaromatic diol, and/or a cycloaliphatic diol which are a diol component(b).

[0076] The present invention No. 23 relates to a polyester blockcopolymer composition as described in the present invention No. 21, inwhich the crystalline aromatic polyester (A1) contains not less than 50%by weight of total of butylene terephthalate and ethylene terephthalateunits.

[0077] The present invention No. 24 relates to a polyester blockcopolymer composition as described in any one of the present inventionNos. 21-23, in which a copolymerization proportion (A1/B) of thecrystalline aromatic polyester (A1) with the lactones (B) is 97/3-50/50by weight.

[0078] The present invention No. 25 relates to a polyester blockcopolymer composition as described in any one of the present inventionNos. 21-24, in which the epoxy compound (C) is a glycidyl type epoxycompound, a compound shown by any one of general formulae (I)-(V)described below, and a mixture thereof.

[0079] (in the formulae, R1, R2, R3 are an alkyl group and, at least oneof those are a methyl group, and total thereof is 8 pieces. Further, “n”is 0-5.)

[0080] The present invention No. 26 relates to a polyester blockcopolymer composition as described in any one of the present inventionNos. 21-25, in which the complex-formable agent for a metal (G) is atleast one kind selected from the group consisting of an oxalic acidderivative, a salicylic acid derivative, and a hydrazide derivative.

[0081] The present invention No. 27 relates to a heat-sensitive body fora heater cable composed of a polyester block copolymer composition asdescribed in any one of the present invention Nos. 21-26.

[0082] The present invention No. 28 relates to a polyester blockcopolymer composition which comprises, in obtaining the polyester blockcopolymer composition by allowing to react the crystalline aromaticpolyester (A1) with the lactones (B), adding and thermally-kneading0.5-5.0 parts by weight of an epoxy compound (C) having one or morepieces of epoxy groups (including at least 0.2 part by weight of two ormore functional epoxy compound) and 0-2.0 parts by weight of acarbodiimide compound (E) to 100 parts. by weight of a polyester blockcopolymer (P3) obtained by allowing to react 0.1-100% by mol at leastthree pieces of at least one kind of a multifunctional compound (D)having at least three pieces of carboxylic group (i), hydroxyl group(ii), and/or an ester-formable group therefrom (iii) with 100% by mol ofa crystalline aromatic polyester (A1).

[0083] The present invention No. 29 relates to a polyester blockcopolymer composition which comprises, in obtaining the polyester blockcopolymer composition by allowing to react the crystalline aromaticpolyester (A1) with the lactones (B), adding and thermally-kneading0.1-5.0 parts by weight of at least one kind of an epoxy compound (C)having one or more pieces of epoxy groups and 0-2.0 parts by weight of acarbodiimide compound (E) to 100 parts by weight of a polyester blockcopolymer (P3) obtained by allowing to react 0.1-200% by mol of at leastone of a multifunctional compound (D) having at least three pieces ofcarboxylic group (i), hydroxyl group (ii), and/or an ester-formablegroup therefrom (iii) with 100% by mol of a crystalline aromaticpolyester (A1).

[0084] The present invention No. 30 relates to a polyester blockcopolymer composition as described in the present invention No. 28 or29, in which the crystalline aromatic polyester (A1) is a polyester ofan aromatic dicarboxylic acid which is an essential acid component (a)and an aliphatic dicarboxylic acid and/or a cycloaliphatic dicarboxylicacid which are optionally added with an aliphatic diol, an aromaticdiol, and/or a cycloaliphatic diol which are a diol component (b).

[0085] The present invention No. 31 relates to a a polyester blockcopolymer composition as described in any one of the present inventionNos. 28-30, in which the crystalline aromatic polyester (A1) containsnot less than 50% by weight of total of butylene terephthalate and/orethylene terephthalate units.

[0086] The present invention No. 32 relates to a polyester blockcopolymer composition as described in any one of the present inventionNos. 28-30, in which a copolymerization proportion of the crystallinearomatic polyester (A1) with the lactones (B) is the same proportion asdescribed in the present invention No. 24.

[0087] The present invention No. 33 relates to a polyester blockcopolymer composition as described in any one of the present inventionNos. 29-32, in which at least one kind of the multifunctional compound(D) contains carboxylic group (i) or an ester-formable group therefrom.

[0088] The present invention No. 34 relates to a polyester blockcopolymer composition as described in any one of the present inventionNos. 28-33, in which the epoxy compound (C) is the same compound asdescribed in the present invention No. 25.

[0089] The present invention No. 35 relates to a polyester blockcopolymer composition as described in any one of the present inventionNos. 28-34, which is employed for blow molding.

[0090] The present invention No. 36 relates to a polyester blockcopolymer composition (R) which comprises, in obtaining the polyesterblock copolymer composition by allowing to react the crystallinearomatic polyester (A1) with the lactones (B), heating a polyester blockcopolymer composition (Q) in a solid phase, and the composition (Q) isobtained by formulating and melt-mixing 0.1-5.0 parts by weight of anepoxy compound (C) having one or more pieces of epoxy groups with 100parts by weight of a polyester block copolymer (P) obtained by allowingto react 0.1-200% by mol of at least one kind of a multifunctionalcompound (D) having at least three pieces of carboxylic group (i),hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with100% by mol of a crystalline aromatic polyester (A).

[0091] The present invention No. 37 relates to a polyester blockcopolymer composition (R) as described in the present invention No. 36,in which the multifunctional compound (D) contains at least one ofcarboxylic group (i) or an ester-formable group therefrom.

[0092] The present invention No. 38 relates to a polyester blockcopolymer composition (R) as described in the present invention No. 36or 37, in which the epoxy compound (C) contains at least one kind of abifunctional epoxy compound.

[0093] The present invention No. 39 relates to a polyester blockcopolymer composition (R) as described in any one of the presentinvention Nos. 36-38, in which the polyester block copolymer composition(R) has an acid value of not more than 0. 5 mgKOH/g and, moreover, amelting point Tm(R) is not more than a temperature of 5° C.-lower than amelting point Tm(P) of the polyester block copolymer (P) before addingthe epoxy compound, that is, Tm(R)≧Tm(P)−5° C.

[0094] The present invention No. 40 relates to a polyester blockcopolymer composition as described in any one of the present inventionNos. 36-39, in which a melt viscosity stability (MI-B)/(MI-A) is 0.5-2.0which is calculated from an MI value (MI-A) in the polyester blockcopolymer composition (R) and an MI value (MI-B) after heating for 10minutes at a temperature selected so as to be a lower temperature in thetemperature described in JIS K7210 which is a temperature of 5°C.-higher than Tm(R).

[0095] The present invention No. 41 relates to a polyester blockcopolymer composition as described in any one of the present inventionNos. 36-40, which is a composition for blow molding.

[0096] The present invention No. 42 relates to a method for thepreparation of a polyester block copolymer composition (R) characterizedin that in obtaining the polyester block copolymer composition byallowing to react the crystalline aromatic polyester (A) with thelactones (B), there is heated a polyester block copolymer composition(Q) in a solid phase, and the composition (Q) is obtained by formulatingand melt-mixing 0.1-5.0 parts by weight of an epoxy compound (C) havingone or more pieces of epoxy groups with 100 parts by weight of apolyester block copolymer (P) obtained by allowing to react 0.1-200% bymol of at least one of a multifunctional compound (D) having at leastthree pieces of carboxylic group (i), hydroxyl group (ii), and/or anester-formable group therefrom (iii) with 100% by mol of a crystallinearomatic polyester (A).

[0097] The present invention No. 43 relates to a method for thepreparation of a polyester block copolymer as described in the presentinvention No. 42, in which heating is conducted in a solid phase atconditions of from a temperature lower than a melting point in a solidphase of the polyester block copolymer composition (R) to a temperaturehigher than a glass transition temperature under an inert gas atmosphereand, moreover, heating is conducted at a temperature (Ta) higher than120° C.

[0098] Tg<Ta<Tm (R), and

[0099] 120° C.<Ta

[0100] The present invention No. 44 relates to a method for thepreparation of a polyester block copolymer as described in the presentinvention No. 42, in which the temperature heating in a solid phase is100- to 5C°-lower than a melting point in a solid phase of the polyesterblock copolymer composition (R) and, moreover, heating is conducted at atemperature (Ta) higher than 150° C.

[0101] Tm(R)−100° C.≦Ta≦Tm(R)−5° C., and

[0102] 150° C.≦Ta

[0103] The present invention No. 45 relates to a method for thepreparation of a polyester block copolymer as described in any one ofthe present invention Nos. 42-44, in which heating is conducted in asolid phase at conditions of,

[0104] (1) a temperature ranges from a temperature lower than a meltingpoint of the polymer to a temperature higher than a glass transitiontemperature in a solid phase and, moreover, preheating is conducted at alower temperature than 150° C. and a temperature (Tb) lower than Ta, andthen,

[0105] (2) a temperature ranges from a temperature lower than a meltingpoint of the polymer to a temperature higher than a glass transitiontemperature in a solid phase and, moreover, heating is conducted at atemperature higher than 120° C.,

[0106] Preheating temperature Tb

[0107] Tg<Tb<Tm(R),

[0108] Tb<150° C., and

[0109] Tb<Ta

[0110] Heating temperature Ta

[0111] Tg<Ta<Tm(R), and

[0112] 120° C.<Ta

BRIEF DESCRIPTION OF DRAWINGS

[0113]FIG. 1 is an outlined drawing which shows an example of astructure in a heater cable.

BEST MODE FOR CARRYING OUT THE INVENTION

[0114] Hereinafter, the present invention No. I will be illustrated indetail.

[0115] The polyester block copolymer (P1) obtained in the presentinvention, if it is a copolymer having a hard segment primarilycontaining the crystalline aromatic polyester (A1) and at leastpartially having a polylactone segment formed by a reaction of thelactones (B), is not particularly limited and, further, in addition toan aliphatic polyether and an aliphatic polyester, it may even containone or more kinds selected from a polyester composed of a combination ofan aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or anoxycarboxylic acid with glycols having a carbon number of 2-12, andwhich has a lower melting point than that of the crystalline aromaticpolyester (A1) as other copolymer segments.

[0116] <Crystalline Aromatic Polyester (A1)>

[0117] The crystalline aromatic polyester (A1) is a polyester of anaromatic dicarboxylic acid which is an essential component and, analiphatic dicarboxylic acid and/or a cycloaliphatic dicarboxylic acidwhich are optionally added as an acid component (a) with an aliphaticdiol, an aromatic diol, and/or a cycloaliphatic diol, and which is apolymer mainly having an ester bond, and which has hydroxyl group and/orcarboxylic group, preferably, hydroxyl group at the molecular terminals.

[0118] <Acid Component (a)>

[0119] As the acid component (a) which constructs the crystallinearomatic polyester (A1), for example, there are specifically enumeratedterephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid,biphenyl dicarboxylic acid, etc., which are an aromatic dicarboxylicacid, and an ester thereof.

[0120] Further, as the aliphatic dicarboxylic acid which is optionallyadded, a dicarboxylic acid having a carbon number of 2-20 is appropriateand, for example, there are specifically enumerated succinic acid,glutaric acid, adipic acid, azelaic acid, sebasic acid, dodecanoicdiacid, and a dimer acid, etc.

[0121] Further, as the cycloaliphatic dicarboxylic acid, for example,1,4-cyclohexane dicarboxylic acid, etc. is enumerated.

[0122] The dicarboxylic acids, in the case of employing as a rawmaterial, may be even an ester, a chloride of an acid, and an anhydride.

[0123] <Diol Component (b)>

[0124] As the diol component (b) for the crystalline aromatic polyester(A1), for example, there are specifically enumerated 1,4-butanediol,1,3-butanediol, 1,2-butanediol, ethyleneglycol, propylene glycol,1,2-propanediol, 1,3-propanediol, 1,5-pentanediol,3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,6-hexanediol, neopentylglycol, and a polymethylene glycol, etc. which are an aliphatic diol.

[0125] Further, as the aromatic diol, for example, there are enumeratedhydroquinone, resorcinol, naphthalene diol, 2,2-bis(4-hydroxyphenyl)propane, an adduct of ethylene oxide and propyleneoxide, etc. to bisphenol A, for example,2,2-bis(4-hydroxyethoxyphenyl)propane, 2,2-bis(4-hydroxydiethoxyphenyl)propane, 2,2-bis(4-hydroxytriethoxyphenyl)propane, and2,2-bis(4-hydroxypolyethoxyphenyl)propane, etc.

[0126] Still further, as the cycloaliphatic diol, for example, there areenumerated 1,4-cyclohexane diol, 1,4-cyclohexane dimethanol,2,2-bis(4-hydroxyethoxycyclohexyl)propane, and an adduct of ethyleneoxide and propylene oxide, etc. to hydrogenated bisphenol A, etc.

[0127] As the crystalline aromatic polyester (A1), for example, thereare specifically enumerated a polyethylene terephthalate, polybutyleneterephthalate, poly-1,4-cyclohexylene dimethylene terephthalate, apolyethylene-2,6-naphthalate, and a polybutylene-2,6-naphthalate, etc.Further, there can be also enumerated a copolymerized polyester in whichthere are further copolymerized an aliphatic dicarboxylic acid unit suchas isophthalic acid, adipic acid, sebasic acid, and dodecanoic diacid,and p-oxybenzoic acid unit with a mixture of the polyesters and thepolyesters. Of those, polybutylene terephthalate is particularlypreferred because of an excellent crystallinity.

[0128] As the crystalline aromatic polyester (A1), there may be employedones produced in a melting state by publicly-known methods without anymodifications, or there may be even employed ones melted again afterhaving once molded into a solid such as pellets and, further, there maybe even employed ones melted after having added the lactones (B)described below.

[0129] <Lactones (B)>

[0130] The lactones (B), if those are a cyclic ester which can bering-opened, are not particularly limited, and there are enumerated avariety of 4 to 12-membered lactones, glycolide, lactide, and a mixturethereof, etc. Of those, there are preferred ε-caprolactone,δ-valerolactone, β-propiolactone, glycolide, and an alkylated productthereof, for example, β-methyl-δ-valerolactone, and lactide, etc.Particularly, ε-caprolactone is preferred from a viewpoint of a thermalstability, a reactivity with the crystalline aromatic polyester, andprofitability.

[0131] As use proportion of both in a reaction of the crystallinearomatic polyester (A1) with the lactones (B), (crystalline aromaticpolyester (A1))/(lactones (B)) ranges in preferably 95/5-20/80, and morepreferably 90/10-30/70. In the case that the crystalline aromaticpolyester (A1) exceeds the upper limit of the use proportion, physicalproperties as a noncrystallinity or low crystallinity resin areinsufficient in a polyester block copolymer (P1) obtained and,contrarily, in the case that it is less than the lower limit of the useproportion, flexibility is unpreferably insufficient as an elastomerresin.

[0132] In the present invention No. I, (B+0.5)% by weight of lactones(B) are introduced into A% by weight of a crystalline aromatic polyester(A1) and, B% by weight of lactones (B) is allowed to react with A% byweight of a crystalline aromatic polyester (A1) to obtain 100% (herein,A+B=100) by weight of the polyester block copolymer (P1), whereby, notlass than 0.5% by weight of unreacted lactones (B) are remained in 100%by weight of the copolymer (P1) after having prepared the polyesterblock copolymer (P1).

[0133] The above value of not less than 0.5% by weight is an amount ofthe unreacted lactones (B) which still remain in a period at which therecompletely terminates a reaction of A% by weight of the crystallinearomatic polyester (A1) with B% by weight of the lactones (B) which areraw materials, and it is a value selected as a basic value of (A+B=100)%by weight. In a higher value exceeding 0.5% by weight, reaction ratebecomes quick. In the case of less than 0.5% by weight, reaction ratebecomes remarkably low, resulting in that practicability is lost.

[0134] It is to be noted that the above-described unreacted lactones area portion of the lactones employed in the reaction, and those remainafter the reaction and, those mean the lactones having a same chemicalstructure as that of the lactones employed.

[0135] Usually, although cyclic esters are thermally produced againafter once having reacted, or form a dimer and a trimer having areactivity, those have a same structure as that in the raw materials,and the unreacted lactones do not include the dimer and the trimer.Reaction mass including the polyester block copolymer (P1) obtained inthe reaction is analyzed by a variety of methods (there is enumerated agas chromatographic analysis described hereinafter), and residualcomponents actually observed are the unreacted lactones.

[0136] In the present invention No. I, the polyester block copolymer(P1), as described hereinabove, contains the hard segment based on thecrystalline aromatic polyester (A1) and the segment based on thelactones (B), and it may further contain even other copolymer segments.A more specific method for the preparation thereof includes acombination of the aliphatic polyether (A2); the polylactone (A3); andthe aromatic dicarboxylic acid, the aliphatic dicarboxylic acid oraliphatic oxycarboxylic acid with glycols having a carbon number of2-12, and there may be even employed a noncrystalline or low crystallinepolyester (collectively referred to as a low crystalline polyester (A4))which is prepared so as to not show an actual melting point in a stateintroduced into the block copolymer together with the crystallinearomatic polyester (A1) and the lactones (B) described hereinabove.

[0137] As the aliphatic polyether (A2), there are enumerated apolyethylene glycol, a polytetramethylene glycol, and a polypropyleneglycol, etc. Of those, the polytetramethylene glycol is particularlypreferred because of an excellent stability and flexibility.

[0138] The polylactone (A3) is a polymer prepared by a ring-openingpolymerization of the lactones (B), there are specifically enumerated apolybutyrolactone, a polyvalerolactone, a polycaprolactone, apolyenantolactone, and a polycaprylolactone, etc. Of those, thepolycaprolactone is preferred from a viewpoint of stability.

[0139] The low crystalline polyester (A4) is an aliphatic polyestercomposed of a combination of the aliphatic dicarboxylic acid oraliphatic oxycarboxylic acid with the glycols having a carbon number of2-12 and, specifically, there are enumerated a polybutylene succinate, apoly-1,6-hexanediol succinate, and a poly-1,6-hexanediol adipate, etc.Of those, the poly-1,6-hexanediol adipate is preferred from a viewpointof stability.

[0140] The low crystalline polyester (A4) is a low crystalline polyesterwhich is prepared so as to not show an actual melting point in the blockcopolymer composed of a combination of the aromatic dicarboxylic acid,aliphatic dicarboxylic acid or aliphatic oxycarboxylic acid with theglycols having a carbon number of 2-12 and, specifically, it is apolyester synthesized by allowing to polycondense or ring-openingpolymerize the aromatic dicarboxylic acid such as terephthalic acid,isophthalic acid, and phthalic acid and an ester-formable derivativethereof, the aliphatic dicarboxylic acid having a carbon number of 2-12or an ester-formable derivative thereof, the diol having a carbon numberof 2-12 or an ester-formable derivative thereof, and the aliphaticoxycarboxylic acid with the glycols having a carbon number of 2-12 with4- to 7-membered lactones.

[0141] <Polyester Block Copolymer (P1)>

[0142] In the above-descriptions, it is essential that the amount of thelactones (B) to be introduce is not less than (B+0.5)% by weight withrespect to A% by weight of the crystalline aromatic polyester (A1), andthe amount of the unreacted lactones is not less than 0.5% by weight.Preferably, the amount of the lactones (B) to be introduce is not lessthan (B+1.0)% by weight, and the amount of the unreacted lactones is notless than 1.0% by weight and, more preferably, the amount of thelactones (B) to be introduce is not less than (B+2.5)% by weight, andthe amount of the unreacted lactones is not less than 2.5% by weight. Inthe case of being less than 0.5% by weight, a melting point lowers inthe polyester block copolymer (P1) obtained and, further, quantity ofheat to fuse decreases, particularly, a fusing peak gets abroad to aside of a lower melting point. On the other hand, in the case that theunreacted lactones exceeds 0.5, the amount is particularly limited,volatile components increase in the case that the polyester blockcopolymer (P1) is molded into pellets, resulting in that a workingcircumstance becomes worse and it becomes difficult to remove theunreacted lactones. Accordingly, it is preferred in not more than 20% byweight, and particularly not more than 10% by weight.

[0143] In the reaction of the crystalline aromatic polyester (A1) withthe lactones (B), although catalysts for a reaction may be employed, thereaction may be even conducted in the absence of the catalysts.

[0144] As the catalysts, there can be employed a catalyst foresterification reaction, a catalyst for a transesterification reactionand a catalyst for a ring-opening polymerization of lactones which arepublicly-known and, specifically, there are enumerated metals such aslithium, potassium, sodium, magnesium, calcium, barium, zinc, aluminum,titanium, cobalt, germanium, tin, antimony, cadmium, manganese, andzirconium, and organic metal compounds thereof, oxides, organic acidsalts, alcolates, and alkoxides, etc. Particularly, there are preferredthe organic metal compounds of tin, aluminum, titanium, zirconium,germanium, antimony, and cobalt, the oxides, organic acid salts,alcolates, and alkoxides, etc. It is to be noted that the catalysts maybe even employed in combination of two or more kinds.

[0145] Temperature in the case that the crystalline aromatic polyester(A1) is allowed to react with the lactones (B), if it is those can reactin a uniformly mixed state under agitation, is not limited. In the casethat the crystalline aromatic polyester (A1) can be dissolved in thelactones (B), those can be sufficiently agitated at a temperature beingnot more than a melting point of the crystalline aromatic polyester(A1). However, in the case that it does not dissolve in the lactones (B)at a temperature being less than the melting point, since adecomposition reaction, etc. of the crystalline aromatic polyester (A1)proceed by heating depending upon the temperature, resulting in thatthere become worse physical properties in the polyester block copolymer(P1) obtained.

[0146] Accordingly, the reaction temperature preferably ranges in 20°C.-lower temperature and 50° C.-higher temperature than a melting pointof the crystalline aromatic polyester (A1) to be employed. If it is thetemperature range, there can be manifested an effect in the presentinvention even in any temperature.

[0147] Reaction time of period in the reaction of the crystallinearomatic polyester (A1) with the lactones (B) is not particularlylimited, if it is a range of a reaction time of period during which thepolyester block copolymer (P1) can be prepared by allowing to react bothcompounds and there can be actualized a method for the preparationthereof in which the amount of the unreacted lactones remained in thepolyester block copolymer (P1) after the reaction can be controlled innot less than 0.5% by weight.

[0148] The reaction time of period in order actualize a method for thepreparation for satisfying conditions in relation to the presentinvention varies depending upon temperature, conditions of agitation,and catalysts, etc., and it is usually 2-300 minutes, more preferably5-120 minutes because productivity becomes worse by a long time reactionof period.

[0149] As an atmosphere in the case of allowing to react the crystallinearomatic polyester (A1) with the lactones (B), an inert gas atmosphereis basically preferred, or a compressed atmosphere not substantiallyhaving a gas phase portion is preferred. Color hue, molecular weight,and hydrolysis resistance, etc. in a resin become worse by the presenceof oxygen and moisture.

[0150] Pressure in the reaction of the crystalline aromatic polyester(A1) with the lactones (B) widely ranges from an ordinary pressure to200 kg/cm₂ or so depending upon a shape of the reaction apparatus. Inthe case that a reaction system is under a compressed state, it isrequired to prevent a leak of oxygen and moisture from outside, and itis preferred to in advance remove gasses and moisture in the crystallinearomatic polyester (A1) with the lactones (B) by publicly-known methods.Specifically, the removal is conducted by combination of a treatment forreducing pressure, purging of an inert gas, and drying operation. In allcases, it is more preferred in the presence of a smaller amount ofoxygen and moisture.

[0151] An apparatus for the reaction of the crystalline aromaticpolyester (A1) with the lactones (B) is not particularly limited, if itis an apparatus in which there can be applied a variety of reactionconditions which include a feed of raw materials and an inert gas, etc.,heating, compressing, mixing and agitation, and discharge, etc.

[0152] As a reaction apparatus for batchwise, there is employed atank-type reaction vessel equipped with agitating blades. It is requiredthat a most appropriate shape of the agitating blades is selected byreaction conditions to be conducted and, usually, a double-helicalribbon blade and a twisted lattice-shape blade, etc. are preferred. As acontinuous reaction apparatus, there can be employed an apparatus, etc.which is excellent in mixing, formation of free surface, and asurface-renewal property in spite of an extruder having one or twoagitating rods or a same shape. Further, a static mixer, etc. isappropriate, and these may be employed in combination of two or morekinds.

[0153] From the polyester block copolymer (P1) obtained by allowing toreact in a variety of modes as described hereinabove, unreacted lactonescan be removed. Even though an operation for removing is conducted,there sufficiently manifests an elevation of a thermal property in thepolyester block copolymer (P1) as an effect by a method for thepreparation in relation to the present invention.

[0154] Removal of the unreacted lactones remained in the polyester blockcopolymer (P1) can be actualized by reducing a pressure under heating orstreaming an inert gas, etc.

[0155] In the removal of the unreacted lactones remained, heatingtemperature is not particularly limited because of being capable ofconducting at a condition of agitating the polyester block copolymer(P1) in a melted state, or even in a state molded into pellets orpowder. In the case of conducting in a melted state, there is preferreda temperature selected from a range of 5- to 50° C.-higher temperaturethan a melting point of the polyester block copolymer (P1). In the caseof exceeding 50° C., a decomposition reaction thermally proceeds, andphysical properties as a resin become worse in the polyester blockcopolymer (P1). On the other hand, in the case of conducting in a statemolded into pellets or powder, there is preferred a temperature range of5- to 100° C.-lower temperature than a melting point of the polyesterblock copolymer (P1) in consideration of avoidance of a blocking problemaccompanied by heating between pellets or powder.

[0156] Specifically, it is preferably selected within a range of100-280° C.

[0157] In the removal of the unreacted lactones remained, a pressure inthe case of-conducting under a reduced pressure is basically morepreferred in a lower range, and it is preferably not more than 200 torr,and more preferably 0.1-50 torr in consideration of profitability.

[0158] On the other hand, in the case of conducting under an inert gasatmosphere which is not under a reduced pressure, including a case ofconducting under streaming the gas, there is preferably employed atypical inert gas such as nitrogen, argon, and helium. However, in thecase of capable of maintaining the polyester block copolymer (P1) at asufficiently low temperature and in the case that a reactionthermally-deteriorated by oxygen does not become problematic, air can bealso employed. Also in the case, it is more preferred to remove moisturein a state as low as possible.

[0159] As an apparatus for removing the unreacted lactones remained, ifit is an apparatus by which the unreacted lactones can be taken out of asystem in a volatile state, it is not particularly limited.

[0160] For example, a batchwise tank-type reaction vessel may be evenmaintain in a reduced pressure state, and there may be continuously orbatchwise employed an apparatus having one or more agitating rods foragitation, surface renewal, and surface formation in a horizontal orvertical column-type reaction vessel. Further, two or more sets of theapparatuses may be employed in combination. In a solid state, there canbe also employed either a column-type apparatus such as a hopper dryer,or an apparatus in which a tank-type reaction vessel can be vibrated orrotated.

[0161] Conditions such as the above-described reaction, temperature,pressure, agitation in relation to the removal of the unreacted lactonesmay be optionally appropriately modified without being maintained untiltermination of an actual synthesis of the polyester block copolymer (P1)or termination of the removal of the unreacted lactones.

[0162] In the case of a method for the preparation in which a batchwiseapparatus is employed, since resins are gradually taken out, and theunreacted lactones are occasionally removed, although an amount of theunreacted lactones fluctuates in every taking out, the amount of theabove-described unreacted lactones remained is a weighted mean value inan amount of unreacted lactones in every resins taken out. On the otherhand, in the case that a removal operation of the unreacted lactones isconducted in an identical apparatus from a total reaction mass withoutgradually taking out resins after a reaction in which a batchwiseapparatus is employed, the amount is shown by an amount of the unreactedlactones immediately before conducting a removal operation.

[0163] In the case that the crystalline aromatic polyester is allowed toreact with the lactones in a continuous reaction apparatus, the amountshows an amount of the unreacted lactones in resins continuously takenout. After that, there is conducted a removal operation of the unreactedlactones.

[0164] An effect by the present invention becomes higher in the casethat at least partial step, particularly, a polymerization step iscontinuously conducted. This depends upon that it is easy to constantlymaintain the amount of the unreacted lactones in relation to the presentinvention in the continuous polymerization process.

[0165] In the present invention, the reaction of the crystallinearomatic polyester (A1) with the lactones (B) may be even conductedunder the presence of an antioxidant and a thermal stabilizer, etc.

[0166] Such the compounds may be added at any one of an initial periodof the reaction, during the reaction, and a final period of thereaction. Further, there may be simultaneously or separately addedadditives such as pigments, a weatherability agent, a metal-cappingagent, fillers, and a modifier together with the above-describedadditives.

[0167] The polyester block copolymer (P1) obtained by the presentinvention No. I can be employed in every uses such as parts for cars,parts for electric equipments, and industrial goods which are molded bymolding methods such as injection molding, extrusion molding, and blowmolding, etc. and, particularly, it is preferably employed for uses suchas a fusibly-cutting layer in a heater cable in which properties inmelting are important.

[0168] Hereinafter, the present invention No. II will be illustrated indetail.

[0169] As described hereinabove, there may be highly-polymerized areaction mass of the polyester copolymer (P1) obtained by the reactionof the crystalline aromatic polyester (A1) with the lactones (B) in thepresent invention No. I in which a fixed amount of the unreactedlactones are remained by a polycondensation of the the polyester blockcopolymer (P) in a solid phase while removing the unreacted lactones, orthe reaction mass may be even highly-polymerized by a polycondensationwhile balancing the reaction of the polyester copolymer with theunreacted lactones in a solid phase without removing the unreactedlactones.

[0170] In the case of removing the unreacted lactones remained thereaction mass of the polyester block copolymer (P1), there can beapplied the method for removing the unreacted lactones, apparatus, andconditions described in the present invention No. I.

[0171] In the second step, reaction in the solid phase is conducted at atemperature not more than a melting point of a polyester block copolymerhaving a high molecular weight (P′1) obtained, and it is preferablyconducted at not more than 5° C.-lower temperature than a melting pointof the polyester block copolymer (P′1) and not less than 130° C. for thepurpose of allowing to proceed a polycondensation reaction whileavoiding a problem such as blocking, and more preferably at not morethan 20° C.-lower temperature than the melting point and not less than150° C.

[0172] In the polycondensation in a solid phase, an atmosphere may beany one of under a reduced pressure or streaming a gas and, as the gas,there are preferred inert gases such as nitrogen, argon, and helium.

[0173] In the case that the gas pressure in the atmosphere is in areduced pressure, it is more preferred in as lower pressure as possible,and it preferably ranges in not more than 200 torr, and more preferably0.01-50 torr.

[0174] Since moisture and oxygen in the inert gases make physicalproperties of resins worse, a smaller amount is more preferred, andthose can be removed by publicly-known means. Reaction time of period ina solid phase can be freely selected by physical properties of resinsobtained, and it usually ranges in 1-50 hours, preferably 6-35 hours,and more preferably 10-24 hours.

[0175] As an apparatus for allowing to react in a solid phase, if it isan apparatus by which the above-described operation can be conducted, itis not particularly limited. For example, there can be also employedeither a column-type apparatus such as a hopper dryer, or an apparatusin which a tank-type reaction vessel can be vibrated or rotated. A morepreferred operation can be conducted by separately arranging anapparatus for removing moisture and alcoholic components such as glycolsproduced by heating and residual volatile components such as unreactedlactones contained in the resins.

[0176] In the case of continuously conducting partial steps,particularly, a step for obtaining the polyester block copolymer (P′1)and a succeeding solid-phase reaction step, an effect by the presentinvention No. II becomes higher. This depends upon that it becomes easyto constantly maintain the amount of the unreacted lactones contained inthe polyester block copolymer (P′1) in the continuous steps.

[0177] In the present invention, from the polyester block copolymerhaving a high molecular weight obtained by allowing to react asdescribed hereinabove, unreacted lactones can be also removed. Eventhough such an operation is conducted, there sufficiently manifests aneffect for elevating a thermal property in the polyester block copolymerhaving a high molecular weight by a method for the preparation inrelation to the present invention. It is to be noted that since theamount of the unreacted lactones remained in the polyester blockcopolymer before being moved to the solid-phase reaction step hasinfluence upon physical properties of the polyester block copolymerhaving a high molecular weight obtained, a preferred polyester blockcopolymer is obtained by in advance adding a fixed amount of lactoneswith respect to the crystalline polyester (A), and there can be adjusteda proportion of units based on the crystalline polyester (A) withrespect to units based on the lactones (B) in the copolymer.

[0178] As a method, etc. for removing the unreacted lactones from areaction product of the polyester block copolymer having a highmolecular weight (P′1), there can be applied a variety of methods,apparatuses, and conditions employed for removing the unreacted lactonesfrom the polyester block copolymer (P1) prepared in the first step ofthe present invention No. I, and the method, etc. may be different fromthe methods employed for removing the unreacted lactones from thepolyester block copolymer (P1).

[0179] The above reaction and conditions for removing the unreactedlactones can be adjusted by changing temperatures, pressures, andagitating conditions, etc. until the polyester block copolymer having ahigh molecular weight (P′1) is actually obtained and the removal of theunreacted lactones terminates.

[0180] The polyester block copolymer having a high molecular weight(P′1) obtained by the present invention No. II can be employed in everyuses such as parts for cars, parts for electric equipments, andindustrial goods which are molded by molding methods such as injectionmolding, extrusion molding, and blow molding, etc. and, particularly, itis preferably employed for uses such as a fusibly-cutting layer in aheater cable in which properties in melting are important.

[0181] Hereinafter, the present invention No. III will be illustrated indetail.

[0182] In the polyester block copolymer (P) to be employed in thepresent invention No. III, a method for the preparation thereof is notparticularly limited, if it is a polyester block copolymer containing ahard segment which is a crystalline aromatic polyester and a softsegment which is a copolymer component composed of an aliphaticpolyether; a polylactone; and an aliphatic polyester, or a copolymercomponent composed of a combination of an aromatic dicarboxylic acid, analiphatic dicarboxylic acid, and an aliphatic oxycarboxylic acid withglycols having a carbon number of 2-12, and the copolymer component iscombined by at least one or more kinds selected from polyesters having alower melting point than that of the crystalline aromatic polyesterwhich constructs the hard segment.

[0183] One of the polyester block copolymer (P) is a polyester blockcopolymer (P1) which is obtained by a reaction of the crystallinearomatic polyester (A1) with the lactones (B). As the copolymer (P1),there can be also employed the polyester block copolymer (P1) or thepolyester block copolymer having a high molecular weight (P′1) shown inthe present inventions No. I and No. II.

[0184] Another one of the polyester block copolymer (P) may be apolyester block copolymer (P2) which is obtained by a condensationand/or ring-opening polymerization of monomer components which constructthe crystalline aromatic polyester (A1), monomer components whichconstruct a low crystalline polyester (A4); an aliphatic polyether (A2);and/or a polylactone (A3).

[0185] As a method for the preparation of the polyester block copolymer(P), for example, there may be a method by a polycondensation of adicarxoxylic acid component or an ester-formable derivative with a diolcomponent, or an ester-formable derivative under the presence of apolymer constructing the soft segment in advance prepared or, even amethod by a polycondensation or a ring-opening polymerization of adicarxoxylic acid and an ester-formable derivative which construct asoft segment, a diol, or an ester-formable derivative, and/or lactonesunder the presence of a polymer constructing the hard segment.

[0186] The above-described methods can be batchwise or continuouslyconducted and, moreover, the polyester block copolymer (P) can beobtained by a tank-type reaction vessel equipped with agitating blades,a column-type reaction vessel equipped with agitating blades, acolumn-type reaction vessel equipped with fixed agitating blades, andeven by an extruder.

[0187] <Hard Segment>

[0188] <Crystalline Aromatic Polyester>

[0189] As the crystalline aromatic polyester (A1) which constructs ahard segment in the present invention, there can be employed the sameones as illustrated in the present invention No. I.

[0190] <Soft Segment>

[0191] In the present invention, an aliphatic polyether (A2), apolylactone (A3), and a low crystalline polyester (A4) construct a softsegment. There can be employed the same ones as illustrated in thepresent invention No. I.

[0192] The above-described respective components which construct thesoft segment have a lower melting point than that of the crystallinearomatic polyester which constructs a hard segment and, in almost cases,it does not show crystallinity in the polyester block copolymer (P). Inthe case that the soft segment is an aliphatic polyester component, atreatment in a melting state ends to proceed a transesterificationreaction in addition to a decomposition reaction by heating, and itunpreferably lowers a melting point in a block copolymer composition(R). In the present invention No. III, since a heating treatment isconducted at a lower temperature, there can be remarkably reduceddecomposition, discoloration, and a decline of a melting point.

[0193] As a proportion of the hard segment component with respect to thesoft segment ranges in preferably 99/1-20/80, and more preferably98/2-30/70 by weight, the hard segment component is composed of thecrystalline aromatic polyester in the polyester block copolymer (P) tobe employed in the present invention No. III, and the soft segment iscomposed of a polyether or aliphatic polyester having a lower meltingpoint than that, (crystalline aromatic polyester)/(constructingcomponents of the soft segment)

[0194] It is to be noted that the hard segment and the soft segment arenot always chemically bonded, and a portion of those may form also amixture.

[0195] In the case that a polycondensation reaction or a ring-openingpolymerization are conducted in order to obtain the polyester blockcopolymer (P), catalysts may be even added and, reactions may be evenconducted under the absence of catalysts. As the catalysts, there can beemployed same ones as described in the present invention No. I.

[0196] <Epoxy Compound (C)>

[0197] The epoxy compound (C), which is allowed to react with thepolyester block copolymer (P) in the present invention No. III, has atleast one epoxy group, and it is not particularly limited in a structurethereof.

[0198] As the epoxy compound (C), there can be employed an epoxycompound (C1) having one epoxy group and an epoxy compound (C2) havingat least two epoxy groups, and both compounds can be employed incombination. For example, there are enumerated a bisphenol type epoxycompound obtained by a reaction of bisphenol A with epichlorohydrin, anovolak type epoxy compound obtained by a reaction of a novolak resinwith epichlorohydrin, glycidyl esters obtained by a reaction of acarboxylic acid with epichlorohydrin, a cycloaliphatic compound-typeepoxy compound obtained from a cycloaliphatic compound, glycidyl ethersobtained from an aromatic compound and epichlorohydrin, an epoxidizedbutadiene, and an epoxy compound obtained from a compound having adouble bond and a peroxide.

[0199] Specifically, there are enumerated an epoxy compound (C1) havingone epoxy group such as methyl glycidylether and phenyl glycidylether,and an epoxy compound (C2) having at least two epoxy groups such asdiethylene glycol diglycidylether, diglycidyl phthalate, diglycidylterephthalate, diglycidyl hexahydrophthalate,3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, an epoxidizedpolybutadiene, and an epoxidized styrene-butadiene-styrene blockcopolymer (an epoxidized SBS).

[0200] In the present invention No. III, addition amount of the epoxycompound (C) depends upon the amount of hydroxyl groups or carboxylicgroups which exist in terminals of the polyester block copolymer (P) orproperties to be required in a composition to be finally obtained, andit is preferably 0.1-5 parts by weight, and more preferably 0.2-3 partsby weight based on 100 parts by weight of the polyester block copolymer(P). In the case that the addition amount of the epoxy compound (C) isless than 0.1 part by weight, an action and effect (particularly, aneffect for elevating heat resistance and hydrolysis resistance) by thepresent invention is not significantly shown and, in a large amount suchas exceeding 5 parts by weight, it adversely affects to surface flatnessand mechanical properties in a molded article.

[0201] The polyester block copolymer (P) is mixed with the epoxycompound (C) in a melted state. A method for mixing thereof is notlimited at all and, if it is a method which is capable of uniformlymixing, any methods can be applied. Temperature of the epoxy compound(C) in melt-mixing ranges in preferably 3° C.- to 60° C.-highertemperature, and more preferably 5° C.- to 40° C.-higher temperaturethan a melting point of the polyester block copolymer (P). In the casethat the temperature in melt-mixing is higher, decomposition reaction isthermally accelerated, whereby, resulting in that heat resistance,hydrolysis resistance, and color hue become worse. In the case that thetemperature in melt-mixing is lower, there become worse crystallizationand dispersion conditions of the epoxy compound (C). Time of period inmelt-mixing is 10 second to 10 minutes or so, preferably, it is set upin 30 second to 5 minutes.

[0202] The reaction of the polyester block copolymer (P) with the epoxycompound (C) can be conducted under the presence of catalysts. There canbe employed all catalysts which can be usually employed in a reaction ofepoxides and, as specific examples, there are enumerated amines,phosphorus compounds such as triphenyl phosphine (TPP), a carboxylicacid, an organic sulphonic acid, sulphuric acid, and an acidic compoundthereof, for example, a metal salts such as alkali metals and alkaliearth metals. Further, the catalysts may be employed in combination oftwo or more kinds.

[0203] The catalysts may be simultaneously added together with the epoxycompound (C) and, may be added after dispersing the epoxy compound (C)into the polyester block copolymer (P) in a melted state or, contrarily,the epoxy compound (C) may be even added after dispersing the catalystsinto the polyester block copolymer (P).

[0204] In the present invention No. III, an effect by the presentinvention can be effectively actualized by mixing one or more kinds ofcompounds selected from the group consisting of a hindered phenol-basedcompound, a sulphur-based compound, a phosphorus-based compound, anamine-based compound, and a hindered amine-based compound as astabilizer.

[0205] Since the stabilizers have an effect for preventing oxidation tothe polyester block copolymer composition or giving a thermal stabilitythereto, those are usually added to the polyester block copolymer (P)which is employed a raw material.

[0206] As specific examples of the stabilizers, there are enumerated analkylated monophenol, for example, 2,6-di-tert-butyl-4-methylphenol,2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol,2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol,2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexcylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol,2,4-dimethyl-6-(1′-methyl-undec-1′-yl)phenol,2,4-dimethyl-6-(1‘-methylheptadecyl-l’-yl)phenol,2,4-dimethyl-6-(1′-methyl-tridec-1′-yl)phenol, and a mixture thereof,alkylthiomethylphenol, for example,2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-didodecylthiomethyl-4-nonylphenol, hydroquinone and an alkylatedhydroquinone, for example, 2,6-di-tert-butyl-4-methoxyphenol,2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone,2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone,2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyphenyl stearate, andbis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate; a cumarone derivative,for example, α-tocopherol. β-tocopherol, γ-tocopherol, δ-tocopherol, anda mixture thereof (vitamin E); a hydroxylated thiodiphenylether, forexample, 2,2′-thiobis(6-tert-butyl-4-methylphenol),2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thio-bis(3,6-di-sec-amylphenol),4,4′-bis-(2,6-dimethyl-4-hydroxyphenyl)disulphide; an alkylidenebisphenol, for example, 2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-(α-methylcyclohexylphenol,2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylidenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylidenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylidenebis(2,6-di-tert-butylphenol),4,4′-methylidenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethyleneglycol=bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butylate],bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methlyphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)-pentane; O-, N- andS-benzyl compounds, for example,3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxybenzylether,octadecyl=4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate,tridecyl=4-hydroxy-3,5-di-tert-butylbenzyl-mercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiophthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulphide,isooctyl=3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate;hydroxybenzylmaloate, for example,2,2-bis(3,5-di-tert-butyl-4-hydroxy-5-methylbenzyl)dioctadecyl maloate,2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)di-dodecylmercaptoethyl=maloate,2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)maloate=bis[4-(1,1,3,3-tetramethylbutyl)-phenyl];a hydroxybenzyl aromatic compound, for example, 1,3, 5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol; a triazinecompound, for example,2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1, 3,5-tris (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate; a benzylphosphonate, for example,2,5-di-tert-butyl-4-hydroxybenzyldimethylphosphonate,3,5-di-tert-butyl-4-hydroxybenzyldiethylphosphonate,3,5-di-tert-butyl-4-hydroxybenzyldioctadecylphosphonate,3,5-di-tert-butyl-4-hydroxy-3-methylbenzyldioctadecylphosphonate,calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylmonoethylphosphonate;an acylaminophenol, for example, lauric 4-hydroxyanilide, stearic4-hydroxyanilide, octyl=N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate;an ester of the following mono or polyvalent alcohol withβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, an example of thealcohol: methanol, ethanol, n-octanol, isooctanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethyleneglycol, 1,2-propanediol,neopentylglycol, thiodiethyleneglycol, diethyleneglycol,triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N′-bis(hydroxyethyl)succinic diamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylol propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane; an ester ofthe following mono or polyvalent alcohol withβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionate, an example of thealcohol: methanol, ethanol, n-octanol, isooctanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethyleneglycol, 1,2-propanediol,neopentylglycol, thiodiethyleneglycol, diethyleneglycol,triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N′-bis(hydroxyethyl)succinic diamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylol propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane; an ester ofthe following mono or polyvalent alcohol withβ-(3,5-dicyclohexyl-4-hydroxyphenyl)propionate, an example of thealcohol: methanol, ethanol, n-octanol, isooctanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethyleneglycol, 1,2-propanediol,neopentylglycol, thiodiethyleneglycol, diethyleneglycol,triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N′-bis(hydroxyethyl)succinic diamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylol propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane; an ester ofthe following mono or polyvalent alcohol withβ-3,5-di-tert-butyl-4-hydroxyphenyl)acetate, an example of the alcohol:methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol,1,9-nonanediol, ethyleneglycol, 1,2-propanediol, neopentylglycol,thiodiethyleneglycol, diethyleneglycol, triethyleneglycol,pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N′-bis(hydroxyethyl)succinic diamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylol propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane;β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic amide, for example,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylene diamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine; anamine-based antioxidant, for example,N,N′-diisopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(naphtyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulphamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphtylamine, N-(4-tert-octylphenyl)-1-naphtylamine,N-phenyl-2-naphtylamine, octylated diphenylamine, for example,p,p′-di-tertiary-butyloctyl diphenylamine, 4-n-butylaminophenol,4-butylylaminophenol, 4-nonanoyl aminophenol, 4-dodecanoylaminophenol,4-octadodecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-d-tertiarybutyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)aminoethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tertiary-octylated N-phenyl-1-naphtylamine, a mixture of a mono- anddialkylated tert-butyl/tert-octyldiphenylamine, a mixture of a mono- anddialkylated tert-butyl/tert-nonyldiphenylamine, a mixture of a mono- anddialkylated tert-butyl/tert-dodecyldiphenylamine, a mixture of a mono-and dialkylated isopropyl/isohexcyldiphenylamine, a mixture of a mono-and dialkylated tert-butyldiphenylamine,2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiadine, phenothiadine, a mixtureof a mono- and dialkylated tert-butyl/tert-octylphenothiadine, a mixtureof a mono- and dialkylated tert-butyloctylphenothiadine,N-allylphenothiadine, N,N,N′,N′-tetrapheyl-1,4-diaminobuto-2-en,N,N-bis(2,2,6,6-tetramethyl-pyperido-4yl)hexamethylenediamine,bis(2,2,6,6-tetramethylpyperido-4yl)sebacate,2,2,6,6-tetramethyl-pyperidine-4-ol; 2-(2′-hydroxyphenyl)benzotriazole,for example, 2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methyl-phenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octylcarbonylethyl)phenyl)-5-chloro-benzotriazole,and a mixture thereof,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole, and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenyl)benzotriazole,and2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-yl-phenol];an esterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethyleneglycol 300; [R—-CH₂CH₂—COO(CH₂)₃—]₂ (in the formula,R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazole-2-yl-phenyl);2-hydroxybenzophenone, for example, 4-hydroxy-, 4-methoxy-, 4-octyloxy-,4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2,4-trihydroxy-, and2′-hydroxy-4,4′-dimethoxy-derivatives; a substituted and nonsubstitutedester of benzoic acid, for example, 4-tert-butylphenyl salicylate,phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol,bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol,3,5-di-tert-butyl-4-hydroxy benzoicacid 2,4-di-tert-butylphenyl,3,5-di-tert-butyl-4-hydroxy benzoic acid hexadecyl,3,5-di-tert-butyl-4-hydroxy benzoic acid2-methyl-4,6-di-tert-butylphenyl; a hindered amine-, for example,bis(2,2,6,6-tetramethyl-4-pyperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-pyperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-pyperidyl)sebacate,n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmaloate=bis(1,2,2,6,6-pentamethyl-4-pyperidyl), a condensation productof 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypyperidine withsuccinic acid, a condensation product of1-N,N′-bis(2,2,6,6-tetramethyl-4-pyperidyl)hexamethylenediamine with4-tert-octyl-amino-2,6-dichloro-1,3,5-triazine,nitrylotriacetictris(2,2,6,6-tetramethyl-4-pyperidyl),1,2,3,4-butanetetracarboxylic acidtetrakis(2,2,6,6-tetramethyl-4-pyperidyl),1,1′-(1,2-ethanedyl)-bis(3,3,5,5-tetramethylpyperadinone)4-benzoyl-2,2,6,6-tetramethylpyperidine,4-stearyloxy-2,2,6,6-tetramethylpyperidine,2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonic acidbis(1,2,2,6,6-pentamethylpyperidyl), 3-n-octyl-7,7,9,9-tetramethyl-1,3,8[4,5]decane-2,4-dion,bis(1-octyoxy-2,2,6,6-tetramethylpyperidyl)sebacate,bis(1-octyoxy-2,2,6,6-tetramethylpyperidyl)succinate, a condensationproduct of N,N′-bis (2,2,6,6-tetramethyl-4-pyperidyl)hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine,acondensationproductof2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethyl-4-pyperidyl)-1,3,5-triazinewith 1,2-bis(3-aminopropylamino)ethane, a condensation product of2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentmethyl-4-pyperidyl)-1,3,5-triazinewith 1,2-bis(3-aminopropylamino) ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspyro[4,5]decane-2,4-dion,3-dodecyl-1-(2,2,6,6-tetramethyl-4-pyperidyl)pyrodine-2,5-dion,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-pyperidyl)pyrodine-2,5-dion, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpyperidines, a condensation product ofN,N′-bis (2,2,6,6-tetramethyl-4-pyperidyl) hexamethylenediamine with4-cyclohexylamino-2,6-di-chloro-1,3,5-triazine, a condensation productof 1,2-bis(3-aminopropylamino)ethane with2,4,6-trichloro-1,3,5-triazine, and4-butylamino-2,2,6,6-tetramethyl-4-pyperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-pyperidyl)-n-dodecylsucsineimide, N-(1,2,2,6,6-pentmethyl-4-pyperidyl)-n-dodecylsucsineimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spyro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxo-spyro[4,5]decanewith epichlorohydrin; 2-(2-hydroxyphenyl)-1,3,5-triazine, for example,2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-3-octloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl)-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine; aphosphite or a phosphonite, for example, triphenyl phosphonite, diphenylphosphonite=alkyl, phenylphosphonite=dialkyl, trisnonylphenylphosphonite, lauryl phosphonite, trioctadecyl phosphonite,distearyl=pentaerythritol=diphosphite, tris (2,4-di-tert-butylphenyl)phosphonite, diisodecyl=pentaerythritol=diphosphite, bis (2,4-di-tert-butyl-4-methylphenyl )=pentaerythritol=diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)=pentaerythritol=diphosphite,bis-isodecyl=pentaerythritol=diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)=pentaerythritol=diphosphite, bis(2,4,6-tri-tert-butyl-6-methylphenyl )=pentaerythritol=diphosphite,tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylenephosphite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocine,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocine, bis (2, 4-di-tert-butyl-6-methylphenyl)methylphosphite, and bis (2, 4-di-tert-butyl-6-methylphenyl ) ethyl phosphite.Of those, tris(2,4-di-tert-butylphenyl)phosphite is preferred.Particularly, tris(2,4-di-tert-butylphenyl)phosphite is preferred.

[0207] Such the compounds may be in advance contained in the polyesterblock copolymer (P), and it may be even simultaneously added togetherwith the epoxy compound (C) or, the epoxy compound (C) may be addedafter dispersing it in the polyester block copolymer (P) in a meltingstate or, contrarily, the compounds may be even dispersed in the epoxycompound (C).

[0208] Further, there may be simultaneously or separately addedadditives such as pigments, a weatherability agent and a metal-cappingagent, fillers, and a modifier in the case of mixing.

[0209] The polyester block copolymer composition (Q) melt-mixed asdescribed hereinabove becomes a polyester block copolymer composition(R) by further thermally-treating in a solid phase.

[0210] Temperature for thermally-treating the polyester block copolymercomposition (Q) is not less than 120° C. and, moreover, a temperatureless than a melting point of the polyester block copolymer composition(Q) obtained by thermally-treating.

[0211] In the case that the temperature for thermally-treating is notless than a melting point of the composition (R), a trouble by meltingresins is caused in handling, and a thermal decomposition reaction isfurther accelerated. Further, in the case that the temperature forthermally-treating is less 120° C., there cannot be almost obtained aneffect of heat resistance and hydrolysis resistance by the presentinvention. More preferably, it is thermally-treated at not less than150° C. and, moreover, at 100- to 5° C.-lower temperature than the amelting point of the composition (R).

[0212] An atmosphere for thermally-treating is selected from inert gasessuch as nitrogen, helium, and argon.

[0213] A minor amount of impurities, particularly, oxygen and moistureare preferably decreased by methods which are usually employed. Such theinert gases may be even constantly streamed through an apparatus inwhich a thermal treatment is conducted and, if a gas atmosphere in theapparatus is nearly filled by the inert gases, a treatment may be evenconducted in a sealed state of the apparatus. Further, an inside of theapparatus may be also maintained at a reduced pressure or a compressedstate in same conditions and, the pressure may be fluctuated during thethermal treatment. In the case of reducing pressure, it is required thatthere is paid attention for volatilization of the various additivesformulated in the polyester block copolymer (P) or the polyester blockcopolymer (R). Preferably, the thermal treatment is conducted whilemaintaining at from 1 torr to an ordinary pressure under a nitrogenatmosphere of not more than 1% by volume of oxygen concentration and notmore than 1% by volume of moisture concentration. Time of period for thethermal treatment is decided according to resin properties required forthe polyester block copolymer composition (R). Usually, it is preferably1-3000 minutes. In the case of a shorter time than 1 minute, an effectby the present invention is very small and a lower time of period lowersproductivity of the polyester block copolymer composition (R) of thepresent invention.

[0214] As an another embodiment for conducting the present invention, itis preferred to preheat the polyester block copolymer composition (Q)obtained by thermally-mixing the polyester block copolymer (P) with theepoxy compound (C) at a lower temperature than the melting point of thecomposition (R) and not more than 150° C. before maintaining at theabove-described temperature for the thermal treatment. By preheating,there can be lowered a decomposition reaction of the polyester blockcopolymer composition (Q) at an initial period of the thermal treatment,resulting in that there can be remarkably shown an effect of an increaseof melt viscosity, etc. in the present invention. In the case, as otherconditions except the temperature, there are applied the same conditionsas in the above-described thermal treatment, and it is preferred thatthe apparatus is not sealed. Further, it can be also conducted at an airatmosphere. In the case that the temperature in the preheating is higherthan 150° C., the above-described effect by the preheating is small and,there is not shown a difference from the case of preheating alone. Amore preferred temperature for the preheating is not more than 120° C.

[0215] The apparatus for conducting the heat treatment and preheating,if it is an apparatus by which the polyester block copolymer composition(Q) can be maintained at a desired time of period, a desired atmosphere,and pressure, is not particularly limited. Those can be conducted incombination of an apparatus which can be operated batchwise orcontinuously with an apparatus for supplying the inert gases, anapparatus for maintaining a reduced pressure, an apparatus for removingimpurities from a discharged gas, and an apparatus for supplying againan inert gas from which the impurities are removed. A cone-blender and ahopper-blender, etc. can be preferably employed.

[0216] The polyester block copolymer composition (R) of the presentinvention can be obtained by thermally-treating the polyester blockcopolymer composition (Q) until being given a certain property.

[0217] <Acid Value>

[0218] An acid value is one of properties which are desired in thepolyester block copolymer composition (R). The acid value is a numericalvalue which is measured by neutralizing acidic components contained inresins using a basic substance such as potassium hydroxide in a statedissolved in solvents, and it is represented by mg number (mgKOH/g) ofpotassium hydroxide to be required for neutralizing 1 g of the resin. Inthe composition (R) of the present invention, the acid value ispreferred in not more than 0.5 mgKOH/g, more preferably not more than0.2 mgKOH/g, and most preferably not more than 0.1 mgKOH/g. In the casethat the acid value is more than 0.5 mgKOH/g, hydrolysis resistancebecomes worse, resulting in that an effect is small in the presentinvention. According to the present invention, thermal decomposition anddiscoloration decrease by a lower temperature for thermally-treating,and such the physical properties can be actualized by a smaller additionamount of the epoxy compound (C).

[0219] Further, there can become suppressed a decline of crystallinitysuch as a decline of a melting point by the addition of the epoxycompound (C).

[0220] <Melt Viscosity Stability>

[0221] Further, another property desired in the polyester blockcopolymer composition (R) is a melt viscosity stability. In the casethat the epoxy compound (C) employed remains in a large amount in anunreacted state, fluctuation of the viscosity is observed by remelting.The melt viscosity stability is represented by formula MI (T, P, andt+10)/MI (T, P, and t). In the formula, the melt index (MI (T, P, andt)) value is a value measured at heating temperature (T), loading (P),and heating time (t) based on a method described in JIS K7210. Herein, Tis not less than 5° C.-higher temperature than the melting point of thecomposition (R), and it is a lowest temperature of experimentaltemperature described in Table 1 of the JIS K7210 and, P is a valueselected so that the MI value becomes a range of 1-30 g/10 minutes. TheMI (T, P, and t+10) value is a value in the case that the heatingtemperature is t+10 minutes at the conditions of the above T and P. Inthe composition (R) obtained in the present invention III, the meltviscosity stability is 0.5-2.0, more preferably 0.75-1.50, and mostpreferably nearly 1.

[0222] By the method of the present invention, since the thermaltreating is conducted at a lower temperature, the remaining epoxycompound (C) can be allowed to sufficiently react while suppressingthermal decomposition and discoloration as low as possible, resulting inthat the viscosity fluctuation can be reduced in a molding process.

[0223] In the polyester block copolymer composition (R) of the presentinvention No. III prepared as described hereinabove, color hue isclearly improved compared to a conventional resin composition obtainedby melt-mixing alone. This depends upon that the treatment in a meltingstate for attaining any one of the two properties can be finished in ashort time in the present invention III.

[0224] <Melting Point>

[0225] In the polyester block copolymer composition (R) prepared by thepresent invention No. III, decline of a melting point is smallercompared to that of a composition (R) prepared by a conventional method,that is, by melt-mixing alone. Melting point (Tm (R)) of the composition(R) is preferably not less than 10° C.-lower temperature than themelting point (Tm (P)) of the polyester block copolymer (P) which is araw material.

[0226] Tm (P)−10° C.≦Tm (R)

[0227] Further, it is preferably not less than 5° C.-lower temperaturethan the melting point (Tm (P)) of the copolymer (P), and morepreferably not less than 3° C.-lower temperature.

[0228] Accordingly, the polyester block copolymer composition (R)obtained by the present invention No. III is more excellent in any oneof heat resistance, hydrolysis resistance, color hue, an increase ofmelt-viscosity and melt-viscosity stability compared to a composition(R) obtained by a conventional method, that is, a composition (R)obtained by melt-mixing alone.

[0229] Hereinafter, the present invention No. IV will be illustrated indetail.

[0230] The present invention No. IV relates to a polyester blockcopolymer composition comprising heating and kneading after formulating0.5-5 parts by weight of a one or more functional epoxy compound (C) and0.01 part by weight to 3.0 parts by weight of a complex-formable agentfor a metal (G) with respect to 100 parts by weight of the polyesterblock copolymer (P1) obtained by allowing to react a crystallinearomatic polyester (A1) with lactones (B).

[0231] First of all, there will be illustrated raw materials foremploying the polyester block copolymer (P1) in relation to the presentinvention No. IV.

[0232] <Crystalline Aromatic Polyester (A1)>

[0233] As the crystalline aromatic polyester (A1) to be employed in thepresent invention No. IV, there can be employed a polyester containingthe same components as the polyesters described in the present inventionNo. III.

[0234] As the crystalline aromatic polyester (A1) to be employed in thepresent invention, there is preferred a polyester having a highpolymerization degree, a melting point of not less than 160° C., and anumber average molecular weight of not less than 5,000.

[0235] Of constructing components in the crystalline aromatic polyester(A1), not less than 60% by weight of butylene terephthalate and/orethylene terephthalate units are desirably contained in consideration ofcrystallinity, heat resistance, or costs of raw materials.

[0236] <Lactones (B)>

[0237] As the lactones (B) for lactone-modifying the crystallinearomatic polyester (A1), there can be employed the same lactones as inthe present invention No. I.

[0238] Hereinafter, there is illustrated the polyester block copolymer(P1) in relation to the present invention No. IV.

[0239] <Polyester Block Copolymer (P1)>

[0240] The polyester block copolymer (P1) in relation to the presentinvention No. IV is obtained by allowing to react the lactones (B) withterminal groups in the above-described crystalline aromatic polyester(A1) by an addition-reaction. Copolymerization ratio (A/B) of thecrystalline aromatic polyester (A1) with the lactones (B) is 97/3-50/50by weight, particularly, preferably 90/10-55/45 by weight. In the casethat the ratio of the lactones (B) is smaller than the range,flexibility of the polyester block copolymer does not manifest,resulting in that it is not appropriate for a heat-sensitive body and,in the case that it is larger than the range, heat resistance lowers inthe polyester block copolymer.

[0241] Further, the crystalline aromatic polyester (A1) can be allowedto react with the lactones (B) through heating and kneading byoptionally adding a catalyst.

[0242] Methods for allowing to react the crystalline aromatic polyester(A1) with the lactones (B), for example, are reported in detail inJP-B-73004115 and JP-B-77049037 Official Gazettes, U.S. Pat. No.2,623,031, JP-B-85004518, JP-B-91077826, and JP-B-88031491 OfficialGazettes, etc.

[0243] Hereinafter, there is illustrated the epoxy compound (C) which isallowed to react with the polyester block copolymer (P1).

[0244] <Epoxy Compound (C)>

[0245] The epoxy compound (C), if it is a compound having at least oneepoxy groups in the molecule, is not particularly limited in thestructure.

[0246] However, a cycloaliphatic or glycidyl ester type epoxy compoundis more preferred than a glycidyl ether type epoxy compound inconsideration of thermal history in formulating or molding acomposition.

[0247] As the cycloaliphatic epoxy compound, although there can bespecifically exemplified compounds shown in general formulae (I)-(V), itis not limited thereto.

[0248] (in the formula, R1, R2, and R3 are an alkyl group, and at leastone of those are a methyl group, and total of carbon numbers is 8pieces. Further, “n” is 0-5.)

[0249] As the glycidyl ester type epoxy compound other than theabove-described (II) and (III)-(V), there are enumerated a mono anddiglycidyl ester of phthalic acid, a mono and diglycidyl ester ofmethyltetrahydro phthalic acid, a mono and diglycidyl ester ofterephthalic acid, a mono, di, and triglycidyl ester of trimelliticacids, and a mono and diglycidyl ester of a dimer acid, etc.

[0250] Further, as the cycloaliphatic epoxy compound other than theabove-described formula (I), there are enumerated Celloxide 2081 (anadduct of ε-caprolactone dimer to3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate), Celloxide2083 (an adduct of ε-caprolactone trimer), Celloxide 2085 (an adduct ofε-caprolactone tetramer), Epolead GT300 and Epolead GT400 (both aretrade name, and obtained by epoxidation of a compound obtained by anesterification of tetrahydrophthalic anhydride with tetrahydrobenzylalcohol or a lactone-modified product thereof) which are manufactured byDaicel Chemical Industries, Ltd., and bis(3,4-epoxycyclohexyl)adipate,etc.

[0251] As the glycidyl ether type ones, there are enumeratedmethylglycidyl ether, phenylglycidyl ether, a polyethylene glycolmonophenylglycidyl ether, ethylene glycol diglycidyl ether, and ethyleneglycol diglycidyl ether, etc.

[0252] In the present invention, there can be employed one or more kindsof the epoxy compounds.

[0253] <Complex-Formable Agent for a Metal (G)>

[0254] As the complex-formable agent for a metal (G) to be formulated inthe polyester block copolymer composition of the present invention IV,there are employed an oxalic acid derivative, a salicylic acidderivative, a hydrazide derivative, and a mixture thereof.

[0255] The complex-formable agent for a metal (G) is not particularlylimited, if it is a compound which forms a metal complex compound withmetal ions which are dissolved out of metals such as copper and a copperalloy which are contact with the polyester block copolymer composition,and it has a structure which is capable of preventing deterioration byoxidation.

[0256] As the oxalic acid derivative, there are enumerated oxalicbisbenzylidene hydrazide andN,N′-bis{2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propyonyloxy]ethyl}oxamide,etc., and as the salicylic acid derivative, there are enumerated3-(N-salicyloyl)amino-1,2,4-triazole and decanedicarboxylic disalicyloylhydrazide, etc. As the hydrazide derivative, there are enumeratedN,N′-bis{2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propyonyloxy]ethyl}hydrazine and bis(2-phenoxypropionyl) hydrazideisophthalate, etc.

[0257] <Polyester Block Copolymer Composition (Q)>

[0258] In the polyester block copolymer composition (Q) in relation tothe present invention IV, formulating amount of the epoxy compound (C)is 0.5-5.0 parts by weight, and preferably 1.0-4.0 parts by weight basedon 100 parts by weight of the polyester block copolymer (P1).

[0259] In the case that the formulating amount is less than 0.5 part byweight, there becomes small an effect for general heat resistance andwater resistance in the composition (Q) obtained, and a thermally-agingresistance in the composition (Q) which comes into contact with PVCremarkably lowers by hydrochloric acid removed from the PVC. Further, inthe case that the formulating amount exceeds 5.0 parts by weight,molding processability occasionally becomes worse by an influence of theunreacted epoxy compound in the composition (Q), and there is shown atendency that surface conditions becomes coarse in a molded articleprepared.

[0260] Formulating amount of the complex-formable agent for a metal (G)is 0.01-3.0 parts by weight, and preferably 0.1-0.5 parts by weightbased on 100 parts by weight of the polyester block copolymer (P1).

[0261] In the case that the formulating amount is less than 0.01 part byweight, a satisfied heat resistance cannot be obtained in thecomposition (Q) which comes into contact with a metal. Further, in thecase that the formulating amount exceeds 3.0 parts by weight, it is noteconomical and, in the composition (Q) which comes into contact with ametal, dispersion possibly becomes worse, unpreferably resulting in thatheat resistance contrarily lowers.

[0262] In the polyester block copolymer composition (Q) in relation tothe present invention IV, there can be also added the stabilizersdescribed in the present invention III.

[0263] Since the stabilizers have an effect for preventing oxidation orthermal stability, those are generally added to the crystalline aromaticpolyester (P1) which is usually employed as a raw material.

[0264] Further, there may be appropriately added additives such aspigments and weatherability stabilizer depending upon uses.

[0265] The composition (Q) is usually obtained by thermally kneading ofthe above formulated resins. Reaction by thermally kneading is usuallyconducted by melt-kneading of resins and, in the case, catalysts may beemployed or not employed.

[0266] As the catalysts, there can be employed all catalysts which canbe usually employed in a reaction of epoxy compounds. For example, therecan be employed solely or in combination of amines, phosphoruscompounds, salts of a monocarboxylic acid or a dicarboxylic acid havinga carbon number of not less than 10 with metals in the Ia and IIa groupsof elementary periodic table.

[0267] Further, temperature for thermally kneading is desirably from atemperature of 5° C.-higher than a melting point of a crystalline of thepolyester block copolymer to 280° C.

[0268] Time of period for kneading is 30 seconds to 60 minutes or so, itcan be appropriately selected according to a kneading style and thetemperature.

[0269] The complex-formable agent for a metal (G), the above-stabilizer,and additives to be formulated in the present invention IV may besimultaneously mixed together with the epoxy compound (C) and, may beindependently mixed.

[0270] The metal which comes into contact with the composition (Q) inthe present invention is not particularly limited, if it is a metalwhich can form a metal complex compound with the complex-formable agentfor a metal (G) such as a succinic acid derivative and a salicylic acidderivative, or a hydrazide derivative and can prevent a deterioratingaction by oxidation, for example, there are enumerated chromium,manganese, iron, cobalt, nickel, copper, zinc, tin, lead, and an alloywhich primarily contains thereof and, in the case of copper and a copperalloy, an effect is particularly remarkable.

[0271] The polyester block copolymer composition (Q) in relation to thepresent invention IV has an excellent heat resistance under a contactwith a metal and PVC. Accordingly, it is preferred as a heat-sensitivebody which comes into direct contact with a short wire composed ofcopper and a copper alloy in a heater cable for an electric blanket andan electric carpet or a heating wire with PVC which is a protectinglayer.

[0272] Hereinafter, the present invention No. V will be illustrated indetail.

[0273] The polyester block copolymer composition (Q) of the presentinvention No. V, in the case of obtaining a polyester block copolymercomposition by allowing to react a crystalline aromatic polyester (A1)with lactones (B), is comprised adding and thermally-kneading 0.5-5.0parts by weight of an epoxy compound (C) having one or more pieces ofepoxy groups and 0-2.0 parts by weight of a carbodiimide compound (E) to100 parts by weight of a polyester block copolymer (P3) obtained byallowing to react 0.1-100% by mol of at least one of a multifunctionalcompound (D) having at least three pieces of at least one kind ofcarboxylic group (i), hydroxyl group (ii), and/or an ester-formablegroup therefrom (iii) with 100% by mol of a crystalline aromaticpolyester (A1).

[0274] First of all, there are illustrated raw materials for preparingthe polyester block copolymer (P3) in relation to the present inventionNo. V.

[0275] <Crystalline Aromatic Polyester (A1)>

[0276] As the crystalline aromatic polyester (A1) to be employed in thepresent invention, there can be employed the same crystalline aromaticpolyester (A1) as in the present invention IV.

[0277] In components for constructing the crystalline aromatic polyester(A1), there are desirably contained not less than 50% by mol of total ofbutylene terephthalate and/or ethylene terephthalate unit inconsideration of crystallinity, heat resistance, and raw material costs.

[0278] <Lactones (B)>

[0279] As the lactones (B) to be employed for lactone-modifying thecrystalline aromatic polyester (A1), there can be employed the same thelactones as in the present invention IV.

[0280] Copolymerization proportion of the crystalline aromatic polyester(A1) with respect to the lactones (B) is preferably 97/3-50/50, and morepreferably 90/10-55/45 in the weight ratio (A/B).

[0281] Further, the crystalline aromatic polyester (A1) can be allowedto react with the lactones (B) by heating and kneading after optionallyadding a catalyst.

[0282] <Multifunctional Compound (D)>

[0283] The multifunctional compound (D) to be employed in the presentinvention V is not particularly limited, if it is an aliphatic and/oraromatic compound having at least three pieces of at least one kind ofcarboxylic group (i), hydroxyl group (ii), and/or an ester-formablegroup therefrom (iii) in the molecule. In the above description, theester-formable group means a derivative of carboxylic group and hydroxylgroup which can react by an esterification reaction, condensationreaction, and addition reaction with the crystalline aromatic polyester(A1) and/or the lactones (B) such as an ester compound from carboxylicgroup (i) and an ester compound from an acid chloride, an acidanhydride, and hydroxyl group (ii).

[0284] As preferred examples of the multifunctional compound (D), therecan be enumerated an aliphatic polycarboxylic acid such as butanetetracarboxylic acid; an aliphatic polyol such as glycerine, trimethylolethane, trimethylol propane (hereinafter, abbreviated as TMP), andpentaerythritol; an aromatic polycarboxylic acid such as trimesic acid,trimellitic acid, 1,2,3-benzene tricarboxylic acid, pyromellitic acid,and 1,4,5,8-naphthalene tetracarboxylic acid; an aromatic polyalcoholsuch as 1,3,5-trihydroxybenzene; an aromatic hydroxycarboxylic acid suchas 4-hydroxy isophthalic acid, 3-hydroxy isophthalic acid, 2,3-dihydroxy benzoic acid, 2,4-dihydroxy benzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxy benzoic acid, protocatec acid,2,4-dihydroxyphenyl acetic acid; and a compound having structural unitsderived from the ester-formable derivatives, etc.

[0285] Hereinafter, there is illustrated the polyester block copolymer(P3) in relation to the present invention No. V.

[0286] <Polyester Block Copolymer (P3)>

[0287] The polyester block copolymer (P3) in relation to the presentinvention No. V can be obtained by allowing to react the crystallinearomatic polyester (A1) and the multifunctional compound (D) with thelactones (B).

[0288] The ratio (A/B) of the crystalline aromatic polyester (A1) withrespect to the lactones (B) is preferably 97/3-50/50, and morepreferably 90/10-55/45 by weight.

[0289] In the case that the ratio of the lactones (B) is too smallerthan the range, flexibility does not manifest in the polyester blockcopolymer composition Q and, in the case that it is too larger than therange, heat resistance lowers.

[0290] The multifunctional compound (D) is added in a range of 0.1-100%by mol, and preferably 2-20% by mol based on 100% by mol of thecrystalline aromatic polyester (A1).

[0291] In the case that addition amount of the multifunctional compound(D) is less than 0.1% by mol, dependence of melt viscosity uponextension rate is insufficient, resulting in that there cannot beobtained a molded article having a uniform thickness in blow moldingand, in the case that it is larger than 100% by mol, decline of meltingpoint is remarkable in an esterification reaction, and only identical orlower heat resistance is obtained to or than inherent heat resistance inthe polyester block copolymer (P3).

[0292] Reaction temperature is 180-270° C., and preferably 230-250° C.

[0293] Reaction pressure is not particularly limited, and it can beconducted at an ordinary pressure.

[0294] Reaction time of period is 0.5-180 minutes, and preferably 5-60minutes.

[0295] Feeding order of raw materials and reaction order are notparticularly limited.

[0296] As an example of a structure in the polyester block copolymer(P3) obtained in the above-described reaction, there is enumerated astructure described below.

[0297] In the structural formula, R is a diol component, R′ is adicarboxylic acid component, R″ is a lactone component, and R′″ is acomponent of the multifunctional compound. “m” is a structural unitnumber of the aromatic polyester, and it is 50-95, “n” is a structuralunit number of the lactones, and it is 5-50. “l” is a structural unitnumber of the multifunctional compound. “l” is 0.001-1 on an average,and it has a broader range in respective compounds.

[0298] In the polyester block copolymer (P3) in relation to the presentinvention, a number average molecular weight is 30,000-100,000, amelting point is 160-250° C., and MI is 0.1-20 g/10 minutes (at 230° C.and 2.16 kgf).

[0299] Hereinafter, the epoxy compound (C) is illustrated which isallowed to react with the polyester block copolymer (P3).

[0300] <Epoxy Compound (C)>

[0301] As the epoxy compound (C) to be employed in the present inventionV, the same epoxy compound (C) can be employed as in the presentinvention IV.

[0302] In the polyester block copolymer composition (Q) in relation tothe present invention No. V, formulating amount of the epoxy compound(C) is 0.5-5.0 parts by weight, and preferably 1.0-4.0 parts by weightbased on 100 parts by weight of the polyester block copolymer (P3). Inthe case that the formulating amount is less than 0.5 part by weight,there becomes small an effect for a general heat resistance and waterresistance in the polyester block copolymer, resulting in that athermally-aging resistance remarkably lowers. In the case that theformulating amount exceeds 5.0 parts by weight, molding processabilityoccasionally becomes worse by an influence of the unreacted epoxycompound, and there is shown a tendency that surface conditions becomecoarse in a molded article prepared.

[0303] From the same reason, two or more functional epoxy compounds mustbe formulated in at least 0.2 part by weight based on 100 parts byweight of the polyester block copolymer (P3).

[0304] <Carbodiimide Compound (E)>

[0305] In the present invention No. V, a carbodiimide compound (E) canbe optionally formulated with the polyester block copolymer composition(Q).

[0306] As the carbodiimide compound, for example, there is enumeratedStabaxol 1 (2,6-diisopropylphenyl diisocyanate dimer) manufactured bySumitomo Bayer Urethane, Ltd., etc.

[0307] Formulating amount of the carbodiimide compound is 0-2.0 parts byweight, and preferably 0.2-1.0 parts by weight based on 100 parts byweight of the polyester block copolymer (P3). If it is not formulated,there is occasionally observed a slight decline of melt viscosity duringa reaction of the epoxy compound (C), and dependence of melt viscosityupon extension rate is insufficient by an influence of an TMP amount,resulting in that there is occasionally obtained a polyester blockcopolymer composition which is not appropriate for blow molding. On theother hand, in the case that it is formulated in exceeding 2.0 parts byweight, discoloration becomes remarkable, and crystallinity lowers inthe polyester block copolymer, resulting in that heat resistance ends tolower.

[0308] <Polyester Block Copolymer Composition (Q)>

[0309] The polyester block copolymer composition (Q) of the presentinvention V is obtained by thermally kneading a formulated mixture inwhich there are formulated the polyester block copolymer (P3), the epoxycompound (C), and optionally the carbodiimide compound (E).

[0310] The above-described reaction by thermally kneading is usuallyconducted by melt-kneading of resins and, in the case, catalysts may beemployed or not employed.

[0311] As the catalysts to be employed in a reaction of the epoxycompound (C), there can be employed the same catalysts as in the presentinvention No. IV.

[0312] Further, temperature for melt-kneading is preferably atemperature of from 5° C.-higher than a melting point of a crystallinein the polyester block copolymer (P3) to 280° C.

[0313] Kneading time of period is 30 seconds to 60 minutes or so, and itis appropriately selected depending upon a mixing style and thetemperature.

[0314] As the catalysts to be optionally added in a reaction of thecarbodiimide compound (E), all catalysts usually employed can beemployed, and the catalysts are optionally employed.

[0315] In the polyester block copolymer composition (Q) in relation tothe present invention No. V, there can be also added the same stabilizeras in the present invention No. III.

[0316] The stabilizers may be usually in advance contained in thecrystalline aromatic polyester resin (P3) which is employed as a rawmaterial because of an effect for preventing oxidation of thecomposition (Q) and thermal stability.

[0317] Further, there may be appropriately even added additives such aspigments and a weatherability stabilizer according to uses.

[0318] It is to be noted that the stabilizer and additives to beformulated in the present invention may be simultaneously mixed togetherwith the epoxy compound (C) and the carbodiimide compound (E), or may beeven independently mixed.

[0319] In the polyester block copolymer composition (Q) of the presentinvention No. v obtained by thermally kneading, a number averagemolecular weight is 50,000-250,000, a melting point is 160-250° C., MIis 0.1-20 g/10 minutes, and a strain-hardening curability is not lessthan 0.1.

[0320] Herein, the strain-hardening curability shows a slope of astraight line obtained by plotting ε and ln(η_(E)/3η*) when η_(E) is avalue obtained by a measurement of extension viscosity, e is strainherein, and η* is a value obtained by a measurement of shear viscosity.

[0321] It is to be noted that in a composition obtained, a portion ofthe epoxy compound may be remained within an extent at which viscositydoes not increase in kneading. Likewise, an unreacted portion of thecarbodiimide compound (E) may be also remained within an extent whichcan be detected by a gas chromatography.

[0322] Hereinafter, the present invention No. VI will be illustrated indetail.

[0323] The polyester block copolymer composition of the presentinvention IV, in obtaining the polyester block copolymer by allowing toreact the crystalline aromatic polyester (A1) with the lactones (B), iscomprised adding and thermally-kneading 0.1-5.0 parts by weight of anepoxy compound (C) having one or more pieces of epoxy groups and 0-2.0parts by weight of a carbodiimide compound (E) to 100 parts by weight ofa polyester block copolymer (P3) obtained by allowing to react 0.1-200%by mol of at least one of a multifunctional compound (D) having at leastthree pieces of at least one kind of carboxylic group (i), hydroxylgroup (ii), and/or an ester-formable group therefrom (iii) with 100% bymol of a crystalline aromatic polyester (A1).

[0324] First of all, there are illustrated raw materials to be employedfor the preparation of the polyester block copolymer (P3) in relation tothe present invention No. VI.

[0325] <Crystalline Aromatic Polyester (A1)>

[0326] As the crystalline aromatic polyester (A1) to be employed in thepresent invention No. VI, there can be employed a polyester having thesame structure as in the crystalline aromatic polyester (A1) in thepresent invention No. IV, and there is preferred a polyester having amelting point of not less than 160° C. in the case of formation of highpolymerization degree.

[0327] Further, as a material for molding, there is preferably prepareda polyester having a number average molecular weight of not less than5,000.

[0328] Of construction components for the crystalline aromatic polyester(A1) exemplified hereinabove, there is preferably employed a polyestercontaining not less than 60% by weight of butylene terephthalate and/orethylene terephthalate units in consideration of crystallinity, heatresistance, or costs for the raw materials.

[0329] <Lactones (B)>

[0330] As the lactones (B) to be employed for lactone-modifying thecrystalline aromatic polyester (A1), there can be employed the samelactones (B) as in the present invention No. IV.

[0331] Copolymerization ratio of the crystalline aromatic polyester (A1)with the lactones (B) is the same as in the copolymerization ratio inthe present invention No. V.

[0332] <Multifunctional Compound (D)>

[0333] As the multifunctional compound (D) to be employed in the presentinvention No. VI, there can be employed the same multifunctionalcompound (D) as in the present invention No. V.

[0334] Addition amount of the multifunctional compound (D) is 0.1-200%by mol, preferably 0.1-150% by mol based on 100% by mol of thecrystalline aromatic polyester (A1).

[0335] In the case that at least one kind of the multifunctionalcompound (D) has carboxylic group (i) or an ester-formable groupthereof, it is added in a range of preferably 0.1-200% by mol, and morepreferably 0.1-150% by mol based on 100% by mol of the crystallinearomatic polyester (A1). In the case, in the case that the additionamount of the multifunctional compound (D) is less than 0.1% by mol,modulus of strain hardening is insufficient, resulting in that there isnot obtained a molded article having uniform thickness in blow moldingand, in the case of exceeding 200% by mol, a decline of a melting pointis remarkable in a transesterification reaction, resulting in that thereis not occasionally obtained only a molded article having an identicalor less heat resistance inherently possessed in a polyester blockcopolymer.

[0336] Further, in the case of the multifunctional compound (D) nothaving carboxylic group (i) or an ester-formable group thereof, themultifunctional compound (D) is added in a range of preferably 0.1-150%by mol, and more preferably 50-120% by mol based on 100% by mol of thecrystalline aromatic polyester (A1). In the case, in the case that theaddition amount of the multifunctional compound (D) is less than 0.1% bymol, modulus of strain hardening is insufficient, resulting in thatthere is not obtained a molded article having uniform thickness in blowmolding and, in the case of exceeding 150% by mol, a decline of amelting point is remarkable in a transesterification reaction, resultingin that there is not occasionally obtained only a molded article havingan identical or less heat resistance inherently possessed in a polyesterblock copolymer. Herein, the modulus of strain hardening means acharacteristic that a melt viscosity increases when an extending rateincreases. Accordingly, when the modulus of strain hardening is larger,since a portion extended in blow molding shows a larger melt viscosity,it is not excessively extended and, since a portion extended shows alower melt viscosity, uniform thickness is obtained. Contrarily, in thecase that the modulus of strain hardening is insufficient, theabove-described effect does not manifest in blow molding, and it tendsto become difficult to obtain a molded article having a uniformthickness.

[0337] Hereinafter, there is illustrated the polyester block copolymer(P3) in relation to the present invention No. VI.

[0338] <Polyester Block Copolymer (P3)>

[0339] The polyester block copolymer (P3) is obtained by allowing toreact the crystalline aromatic polyester (A1) and the multifunctionalcompound (D) with the lactones (B).

[0340] Ratio of the crystalline aromatic polyester (A1) with thelactones (B) and reaction conditions are the same as in the presentinvention No. V.

[0341] Subsequently, the epoxy compound (C) is illustrated which isallowed to react with the polyester block copolymer (P3).

[0342] <Epoxy Compound (C)>

[0343] As the epoxy compound (C) to be employed in the present inventionNo. V, there can be employed the same epoxy compound (C) as in thepresent invention No. IV.

[0344] In the polyester block copolymer composition (Q) in relation tothe present invention No. VI, formulation amount of the epoxy compound(C) is 0.1-5.0 parts by weight, and preferably 0.25-3.0 parts by weightbased on 100 parts by weight of the polyester block copolymer (P3). Inthe case that the formulation amount is less than 0.1 part by weight,there becomes small an effect to general heat resistance and waterresistance in the polyester block copolymer, and thermally-agingresistance remarkably lowers. In the case that the formulation amountexceeds 5 parts by weight, there is a tendency that moldingprocessability occasionally becomes worse by an influence of theunreacted epoxy compound, or surface conditions becomes coarse in amolded article.

[0345] <Carbodiimide Compound (E)>

[0346] In the present invention VI, the same carbodiimide compound (E)as in the present invention V can be optionally formulated in the sameweight ratio in the polyester block copolymer composition.

[0347] <Polyester Block Copolymer Composition (Q)>

[0348] The polyester block copolymer composition (Q) of the presentinvention VI is obtained by thermally kneading a blend composed of thepolyester block copolymer (P3), the epoxy compound (C) and, optionally,the carbodiimide compound (E).

[0349] The reaction by thermally kneading is usually conducted bymelt-mixing and, in the case, catalysts may be not employed, or may beeven employed.

[0350] As the catalysts to be employed in the reaction of the epoxycompound (C), the same catalysts can be employed as in the presentinvention IV.

[0351] In the composition (Q) obtained in the present invention VI, thesame stabilizers can be added as in the present invention III.

[0352] Further, additives such as pigments and weatherability agents maybe appropriately added depending upon uses.

[0353] Mixing of the above-described stabilizer and additives may besimultaneously or separately conducted together with mixing of theabove-described epoxy compound (C) or the carbodiimide compound (E).

[0354] In the polyester block copolymer composition (Q) of the presentinvention VI, a number average molecular weight is 40,000-110,000, amelting point is 180-230° C., and MI is 0.1-10 g/10 minutes, and it hasa large modulus of strain hardening.

[0355] As a result, it has a characteristic of an exceedingly lessgeneration of flashes in molding, in addition to capability of providinga molded article having uniform thickness in blow molding. Moreover, amolded product obtained using the composition is very excellent also inheat resistance in addition to inherent properties in a polyester blockcopolymer and, even though it is employed in a use exposed to hightemperature for a long time of period, it can give a very excellentphysical property to a molded article.

[0356] Hereinafter, the present invention No. VII will be illustrated indetail.

[0357] The polyester block copolymer composition (R) of the presentinvention VII, in the case of obtaining the polyester block copolymer byallowing to react the crystalline aromatic polyester (A1) with thelactones (B), is comprised heating in a solid condition a polyesterblock copolymer composition (Q) obtained by adding and thermally mixing0.1-5.0 parts by weight at least one kind of an epoxy compound (C)having one or more pieces of epoxy groups to 100 parts by weight of apolyester block copolymer (P) obtained by allowing to react 0.1-200% bymol of at least one kind of a multifunctional compound (D) having atleast three pieces of carboxylic group (i), hydroxyl group (ii), and/oran ester-formable group therefrom (iii) with respect to 100% by mol of acrystalline aromatic polyester (A).

[0358] The polyester block copolymer (P) in relation to the presentinvention is obtained by a reaction of the crystalline aromaticpolyester (A1) with the lactones (B).

[0359] <Crystalline Aromatic Polyester (A1)>

[0360] The crystalline aromatic polyester (A1) to be employed in thepresent invention is a polymer primarily having ester bonds, and it hashydroxyl groups at a portion of molecular terminals, and the same onesare employed as in the present invention VI.

[0361] <Lactones (B)>

[0362] The lactones (B) to be employed in the present invention VII isthe same ones as in the present invention VI.

[0363] Copolymerization proportion of the crystalline aromatic polyester(A1) with the lactones (B) is 97/3-50/50, and preferably 90/10-55/45 byweight ratio.

[0364] Further, the crystalline aromatic polyester (A) can be allowed toreact with the lactones (B) by thermally mixing using optionallycatalysts. In the case that the proportion of the lactones (B) is toosmaller than the range, ductility does not manifest in the polyesterblock copolymer (P), and in the case of being too larger than the range,heat resistance lowers in the polyester block copolymer (P) and thepolyester block copolymer composition (R) obtained.

[0365] <Multifunctional Compound (D)>

[0366] The multifunctional compound (D) to be employed in the presentinvention is the same as in the present invention No. VI.

[0367] Addition amount of the multifunctional compound (D) is 0.1-200%by mol, preferably 0.1-150% by mol based on 100% by mol of thecrystalline aromatic polyester (A).

[0368] In the case that the multifunctional compound (D) does not havecarboxylic group (i) or an ester-formable group thereof, it is added ina range of preferably 0.1-150% by mol, and more preferably 50-120% bymol based on 100% by mol of the crystalline aromatic polyester (A1). Inthe case that the addition amount of the multifunctional compound isless than 0.1% by mol, the modulus of strain hardening is insufficient,resulting in that there is not obtained a molded article having uniformthickness in blow molding and, in the case of exceeding 150% by mol, adecline of a melting point is remarkable in a transesterificationreaction, resulting in that there is not occasionally obtained only amolded article having an identical or less heat resistance inherentlypossessed in a polyester block copolymer.

[0369] Further, in the case that the multifunctional compound (D) has atleast one of carboxylic group (i) or an ester-formable group thereof, itis added in a range of preferably 0.1-200% by mol, and more preferably50-150% by mol based on 100% by mol of the crystalline aromaticpolyester (A1). In the case that the addition amount of themultifunctional compound is less than 0.1% by mol, the modulus of strainhardening is insufficient, resulting in that there is not obtained amolded article having uniform thickness in blow molding and, in the caseof exceeding 200% by mol, a decline of a melting point is remarkable ina transesterification reaction, resulting in that there is notoccasionally obtained only a molded article having an identical or lessheat resistance inherently possessed in a polyester block copolymer.

[0370] Subsequently, there will be illustrated the polyester blockcopolymer (P) in relation to the present invention.

[0371] <Polyester Block Copolymer (P)>

[0372] The polyester block copolymer (P) in relation to the presentinvention is obtained by allowing to react the crystalline aromaticpolyester (A1) having terminal hydroxyl groups, the multifunctionalcompound (D), and the lactones (B).

[0373] Reaction temperature is 180-270° C., and preferably 230-250° C.

[0374] Reaction pressure is not particularly limited, and reaction canbe conducted at an ordinary pressure.

[0375] Reaction time of period is 0.5-600 minutes, and preferably 5-120minutes.

[0376] Feeding order of raw materials and reaction order are notparticularly limited.

[0377] In the polyester block copolymer composition (P) in relation tothe present invention, a number average molecular weight is20,000-100,000, a melting point is 160-250° C., and MFR is 0.1-50 g/10minutes (230° C., 2.16 kgf).

[0378] The epoxy compound (C) to be allowed to react with the polyesterblock copolymer (P) is the same as in the present invention VI.

[0379] Formulation amount of the epoxy compound (C) is 0.1-5.0 parts byweight, and preferably 0.25-3.0 parts by weight based on 100 parts byweight of a polyester block copolymer (P). In the case that theformulation amount is less than 0.1 part by weight, there becomes smallan effect to general heat resistance and water resistance in thepolyester block copolymer, and thermally-aging resistance remarkablylowers. In the case that the formulation amount exceeds 5.0 parts byweight, there is a tendency that molding processability occasionallybecomes worse by an influence of the unreacted epoxy compound, orsurface conditions becomes coarse in a molded article.

[0380] <Polyester Block Copolymer Composition (Q)>

[0381] The polyester block copolymer composition (Q) of the presentinvention VI is obtained by thermally kneading a mixture composed of thepolyester block copolymer (P) and the epoxy compound (C).

[0382] Mixing of the epoxy compound (C) with the polyester blockcopolymer (P) is usually conducted by melt-mixing and, a method for themixing is not limited at all, if it is a method capable of uniformlymixing, any methods may be applied.

[0383] Temperature in melt-mixing of the epoxy compound ranges inpreferably 3° C.- to 60° C.-higher temperature, and more preferably 5°C.- to 40° C.-higher temperature than a melting point of the polyesterblock copolymer. In the case that the temperature in melt-mixing ishigher, decomposition reaction is thermally accelerated, whereby,resulting in that heat resistance, hydrolysis resistance, and color huebecome worse. In the case that the temperature in melt-mixing is lower,dispersion conditions of the epoxy compound become worse. Time of periodin melt-mixing is 10 second to 10 minutes or so, preferably, it is setup in 30 second to 5 minutes. Compared to a conventional method, thatis, a method by melt-mixing alone, since a treatment at a lowertemperature can be conducted and evaporation components can bedecreased, a working circumstance can be improved.

[0384] <Polyester Block Copolymer Composition (R)>

[0385] Conditions are as follows at which the polyester block copolymercomposition (Q) is thermally treated in a solid phase for obtaining thepolyester block copolymer composition (R).

[0386] As the conditions for thermally treating in a solid phase,heating temperature (Ta) ranges in from a lower temperature than amelting point of the polyester block copolymer composition (R) to ahigher temperature than a glass transition point of the polyester blockcopolymer composition (R) under an inert gas atmosphere and, moreover,it is a higher temperature than 120° C.

[0387] Tg<Ta<Tm (R), and

[0388] 120° C.<Ta

[0389] In the case that the epoxy compound (C) contains at least onekind of a bifunctional epoxy compound, heating temperature (Ta) in asolid phase is 10° C.- to 5° C.-lower than a melting point of a polymerin a solid phase and higher than 150° C.

[0390] Tm(R)−100° C.≦Ta≦Tm(R)−5° C., and

[0391] 150° C.≦Ta

[0392] Heating in a solid phase can be conducted by two stages describedbelow.

[0393] (1) after having preheated at a temperature (Tb) lower than 150°C. and lower than Ta which is in a temperature range from a temperaturelower than a melting point of a polymer in a solid phase to atemperature higher than a glass transition point of the polymer,

[0394] (2) heated at a temperature (Ta) which is in a temperature rangefrom a temperature lower than a melting point of a polymer in a solidphase to a temperature higher than a glass transition point of thepolymer, and higher than 120° C.

[0395] Preheating temperature Tb

[0396] Tg<Tb<Tm (R),

[0397] Tb<150° C., and

[0398] Tb≦Ta

[0399] Heating temperature Ta

[0400] Tg<Ta<Tm (R), and

[0401] 120° C.<Ta

[0402] In the case, catalysts may be not employed or even employed.

[0403] As the catalysts, there can be employed all catalysts which canbe usually employed in a reaction of epoxy compounds. For example, therecan be employed solely or in combination of amines, phosphoruscompounds, salts of a monocarboxylic acid or a dicarboxylic acid havinga carbon number of not less than 10 with metals in the Ia and IIa groupsof elementary periodic table. Such the catalysts may simultaneously addtogether with the epoxy compound, or may even add after having inadvance dispersed the epoxy compound into the polyester block copolymerin a melting state or, contrarily, the catalysts may be in advance evendispersed.

[0404] In the polyester block copolymer composition (R) of the presentinvention, an acid value is not more than 0.5 mgKOH/g, a melting pointTm (R) is a temperature of not more than 5° C.-lower temperature than amelting point Tm (P) in the polyester block copolymer composition (P)before adding the epoxy compound.

[0405] Tm (R)≧Tm (P)−5° C.

[0406] In the polyester block copolymer composition, a temperature foran MI value test is not less than 5° C.-higher than a melting point ofthe composition, and it is a lowest temperature of an experimentaltemperature described in Table 1 of JIS K7210 and, moreover, a meltviscosity stability {(MI-B)/(MI-A)} is 0.5-2.0, which is calculated froman MI value (MI-A) measured at experimental conditions selected so thatan experimental loading becomes a range of an MI value of 1-30 g/10minutes and an MI value (MI-B) at the same experimental temperature andthe same experimental loading as in a measurement of the (MI-A) afterheating for 10 minutes from an initiation of measurement of the MI-Avalue at the same experimental temperature as in a measurement of theMI-A value.

[0407] In the polyester block copolymer composition (R), a numberaverage molecular weight is 40,000-200,000, a melting point is 150-280°C., MI is 0.01-5, and modulus of a strain-hardening is not less than0.1-2.4. Herein, the modulus of a strain-hardening shows a slope of astraight line obtained by plotting ε and ln(η_(E)/3η*) when η_(E) is avalue obtained by a measurement of extension viscosity, ε is strainherein, and η* is a value obtained by a measurement of shear viscosity.

[0408] In the polyester block copolymer composition (R), there can beadded a stabilizer such as a hindered phenol-based compound, aphosphite-based compound or an organic composite phosphite, and acarbodiimide compound. Since the stabilizers have an effect forprevention of oxidation or thermal stability in the polyester blockcopolymer composition, those are usually added to polyester-basedresins. Further, additives such as pigments and weatherabilitystabilizers may be appropriately even added depending upon uses.

[0409] Mixing of the stabilizers and additives to be formulated in thepresent invention may be simultaneously conducted when the epoxycompound is mixed, or may be even independently conducted.

[0410] In the polyester block copolymer composition (R) obtained in thepresent invention, the modulus of strain hardening is large, and therecan be obtained a molded article having uniform thickness in blowmolding and, further, a change ratio of melt viscosity by thermalhistory is small and a resin can be reused. Further, color hue is moreimproved than in a reaction proceeded in a melting state owing to acharacteristic that a reaction with the epoxy compound (C) is conductedby heating in a solid phase and, furthermore, a large melt viscosity canbe obtained, resulting in that a large-size molded article can be alsoobtained in blow molding. Also, it has a characteristic that productionof flashes in molding is exceedingly slight. Moreover, a molded articleobtained using the composition (R) is very excellent also in heatresistance in addition to properties shown in a polyester blockcopolymer and, even though it is employed for uses exposed to a hightemperature for a long time of period, it does not cause heatdeterioration, and it can provide a molded article having very excellentphysical properties.

EXAMPLES

[0411] Hereinafter, although the present invention will be specificallyillustrated by Examples, the present invention is not limited thereto.In the Examples, mere part means part by weight.

[0412] Hereinafter, there were measured as follows an acid value, anunreacted lactone amount, a polycaprolactone content in resins, an MIvalue, a melt viscosity stability, a tensile strength and extension,thermal properties (a melting point, a melting peak temperature, aninitiating temperature of melting), color hue, hydrolizability, and heatresistance stability.

[0413] Unreacted Lactone Amount:

[0414] Using GC-14A manufactured by Shimadzu, there was employed aglass-made column having an internal diameter of 3.2 mm and length of2.1 m, and in which there is filled [PEG20M (a liquid for a fixed bed)10%]/[Uniport HPS (carrier)]. 1 g of a sample and 0.05 g ofdiphenylether which is an internal standard substance were preciselyweighed, followed by dissolving into HFIP(hexafluoroisopropanol).Measurement was conducted at the constanttemperature of 180° C. using nitrogen as a carrier gas, unreactedlactone amount (% by weight) was calculated by an internal standardmethod based on results obtained.

[0415] Polycaprolactone Content in the Polyester Block Copolymer (P1):

[0416] The residual unreacted lactone was removed from the polyesterblock copolymer (P1), and a polymer obtained was dissolved in a solventHFIP/CDCl₃ (heavy chloroform)=9/1 which contains a small amount oftetramethylsilane, and there was measured the component ratio of apolybutylene terephthalate with respect to a polycaprolactone by aproton NMR.

[0417] It was confirmed that the polycaprolactone content in thepolyester block copolymer (P1) is in a range of 59.9/40.1 to 60.3/39.7in all resins in the present invention I.

[0418] MI Value:

[0419] It was measured at a sample temperature of 230° C. in heating anda loading of 2,160 kgf according to JIS K7210.

[0420] The above value are employed even as a value of T:230° C. andP:2,160 kgf in the following MI value (T, p, t).

[0421] Melt Viscosity Stability:

[0422] The melt viscosity stability is shown by MI (T, p, t+10)/MI (T,p, t). In the equation, the Melt Index (MI (T, p, t)) value is a valueat a heating temperature (T), loading (P), and heating time of period(t) which are described in the JIS K7210, and T is not less than 5°C.-higher temperature than a melting point of the composition (R), andit is a lowest temperature of experimental temperature described inTable 1 of the JIS K7210. P is a value selected so that MI value becomesa range of 1-30 g/10 minutes.

[0423] MI (T, P, t+10) is a value when heating time of period is set upat t+10 minutes in the above conditions T and P.

[0424] In the Examples described below, specifically, T is 230 C, P is2.16 kgf, and “t” is a time of period regulated in JIS.

[0425] Tensile Strength and Extension:

[0426] Tips were molded into a plain plate having the thickness of 2 mmusing a heating press, and Dumbbell No. 3 test piece was punched, andthe test piece was extended at the speed of 200 m/minutes, and strengthis shown by a value in which a load (kgf) at break is divided by aninitial cross sectional area (cm₂), the extension ratio (%) is aproportion of extension in the original test piece with respect tolength of an original test sample.

[0427] Melting Point:

[0428] Melting point is a peak temperature in melting measured by adifferential scanning calorimeter (DSC) apparatus according to JISK7121.

[0429] Color Hue:

[0430] Yellow Index (YI) value was measured by a color difference meterΣ-90 manufactured by Nihon Denshoku Kogyo.

[0431] Acid Value:

[0432] Sample was dried at 100° C. and a reduced pressure for 20 hours,followed by weighing 1.0 g and thermally dissolving in 50 g of benzylalcohol at 160° C. After having cooled by water, 50 g of chloroform wasadded and mixed. Using phenol phthalein as an indicator, titration wasconducted by a {fraction (1/10)} normal KOH ethanol solution. There weredecided values at 0 minute by an extrapolation method from appropriatethree points in which dissolving time of period is 10-30 minutes and, avalue in which an acid value in a mixture of benzyl alcohol withchloroform was taken off from the values employed as an acid value(mgKOH/g) of the samples. The acid value in the mixture was separatelymeasured.

[0433] Hydrolysis Resistance:

[0434] The plain plate having the thickness of 2 mm prepared by moldingthe tips using a heating press was immersed in hot water of 95° C. for 7days to hydrolyze, and Dumbbell No. 3 test pieces were punched from theplate. Test pieces were extended at speed of 200 mm/minute, a value inwhich load (kg) at break was divided by an initial cross sectional area(cm₂) is shown as a strength (kg/cm₂), and the extension ratio (%) isshown as a proportion of extension in the test piece until a break withrespect to length of an original test sample. The extension ratio in thecase of not conducting a hydrolysis treatment is shown as 100%, and itis compared to an extension ratio in the case of having broken.

[0435] Heat Resistance Stability:

[0436] The plain plate having the thickness of 2 mm prepared by moldingthe tips using a heating press was placed in a gear oven adjusted to165° C. for 14 days to thermally-treat, and Dumbbell No. 3 test pieceswere punched from the plate. Test pieces were extended at speed of 200mm/minute, and a value in which load (kgf) when having broken wasdivided by an initial cross sectional area (cm₂) is shown as a strength(kgf/cm₂), and the extension ratio (%) is shown as a proportion ofextension in the test piece until a break with respect to length of anoriginal test sample. The extension ratio in the case of not beingthermally treated is shown as 100%, and it is compared to an extensionratio in the case of having broken.

[0437] Modulus of Strain Hardening:

[0438] It is shown as a slope of a straight line obtained by plotting εand ln(η_(E)/3η*) when η_(E) is a value obtained by a measurement ofextension viscosity at a constant strain rate and 230° C., ε is strainherein, and η* is a value obtained by a measurement of shear viscosity.Results are shown as follows. In the case that the slope is not lessthan 1.0, a sample shows (⊚) the modulus of strain hardening, in thecase that the slope is less than 1.0, a sample slightly shows (∘) themodulus of strain hardening, and in the case that the slope is 0, asample does not show (x) the modulus of strain hardening. It is to benoted that it is shown by a value in the case of the present inventionVII.

[0439] Draw Down Property:

[0440] Capirograph manufactured by Toyo Seiki was equipped with acapillary having a diameter of 3 mm and length of 10 mm, and a resin wasextruded at 240° C. and an extruding rate of 20 mm/min. A time of periodwhen a strand is 300 mm-extended was compared to a time of period when astrand is 60 mm-extended to calculate the ratio. For blow molding, it ispreferred that the ratio is not less than 3.

[0441] Feeding Molar Ratio (A:D):

[0442] Addition ratio % by mol of the multifunctional compound (D) wascalculated from a number average molecular weight of the polyester (A)measured by GPC based on a standard polymethyl methacrylate (PMMA), anda formulating mol amount of the (A) was decided based thereon. Supposingthat the formulating mol amount of the (A) is 100% by mol, the additionratio % by mol of the multifunctional compound (D) is decided in a rangeof 0.01-5.0% by mol depending upon uses.

[0443] As a column in the GPC, there were employed Shodex GPC HFIP-800P,HFIP-805P, HFIP-804P, and HFIP-803P manufactured by Showa Denko, Ltd.,and RID-6A manufactured by Shimadzu Seisakusyo was employed as adetector. As an elution liquid, hexafluoro isopropanol was employed, anda measurement was conducted at a column temperature of 50° C. and a flowrate of 1.0 ml/min.

[0444] <Raw Material>

[0445] Crystalline Aromatic Polyester:

[0446] As the crystalline aromatic polyester, there was employed apolybutylene terephthalate (PBT) described below having hydroxyl groupsat terminals of a molecule.

[0447] PBT (A1) employed in the present invention I is a commerciallysupplied polybutylene phthalate having a melting point of approximately230° C. which is composed of terephthalic acid and isophthalic acidwhich are an acid component and 1,4-butane diol which is a glycolcomponent, and which has a number average molecular weight of 39,000.

[0448] PBT (A1) employed in the present invention II is a commerciallysupplied polybutylene phthalate having a melting point of approximately230° C. which is composed of terephthalic acid and isophthalic acidwhich are an acid component and 1,4-butane diol-which is a glycolcomponent, and which has a number average molecular weight of 35,000.

[0449] PBT (A1) employed in the present invention III is a commerciallysupplied polybutylene phthalate having a melting point of approximately230° C. which is composed of terephthalic acid and isophthalic acidwhich are an acid component and 1,4-butane diol which is a glycolcomponent, and which has a number average molecular weight of 31,000.

[0450] PBT (A1) employed in the present invention IV is a commerciallysupplied polybutylene phthalate having a melting point of approximately205° C. which is composed of terephthalic acid and isophthalic acidwhich are an acid component and 1,4-butanediol which is a glycolcomponent, and which has a number average molecular weight of 35,000.

[0451] Likewise, PBT (A₂) is a commercially supplied polybutylenephthalate having a melting point of approximately 185° C. which iscomposed of terephthalic acid and isophthalic acid which are an acidcomponent and 1,4-butanediol which is a glycol component, and which hasa number average molecular weight of 35,000.

[0452] PBT (A1) employed in the present invention V is a commerciallysupplied polybutylene phthalate having a melting point of approximately230° C. which is composed of terephthalic acid and isophthalic acidwhich are an acid component and 1,4-butanediol which is a glycolcomponent, and which has hydroxyl groups at terminals of a molecule andhas a number average molecular weight of 39,000. However, PBT (A1)employed in Comparative Example V-I is a commercially suppliedpolybutylene phthalate having a melting point of approximately 230° C.which is composed of terephthalic acid and isophthalic acid which are anacid component and 1,4-butanediol which is a glycol component, and whichhas a number average molecular weight of 35,000.

[0453] PBT (A₁) employed in the present inventions VI and VII is acommercially supplied polybutylene phthalate having a melting point ofapproximately 230° C. which is composed of terephthalic acid andisophthalic acid which are an acid component and 1, 4-butanediol whichis a glycol component, and which has a number average molecular weightof 39,000.

[0454] Abbreviations of Substances to be Formulated:

[0455] Phenylglycidyl ether (GPE)

[0456] Kardular E-10 (a glycidyl type monoepoxy compound)

[0457] Bisphenol F diglycidyl ether (BFDGE)

[0458] Cyclohexane dicarboxylic acid diglycidyl ester (CHDDG)

[0459] 3,4-epoxycy clohexylmethyl-3,4-epoxycyclohexanecarboxylate(Clloxide 2021P manufactured by Daicel Chemical Industries, Ltd.)

[0460] Triphenylphosphine (TPP)

[0461] Tetraxis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane (a trade name: Irganox 1010)

[0462] Reaction Vessel for Synthesis of a Polyester Block Copolymer:

[0463] As the reaction vessel for synthesis of a polyester blockcopolymer, there was employed a vessel equipped with an agitator, athermometer, a condenser, and a line for distilling out.

[0464] Extruder for Kneading:

[0465] There was employed a 32 mm φ twin-screw extruder (merelyabbreviated as an extruder).

[0466] Conditioned Test Piece:

[0467] From a polyester block copolymer composition, a sheet havingthickness of 1 mm was prepared by compression molding, and a tensiletest piece having thickness of 1 mm was prepared by punching, which isshown in JIS K7113 No. 2.

[0468] The test piece was placed in an oven set up at a temperature of140° C., and sampling was conducted with a time lapse, and it wasemployed as a conditioned test sample after having placed in a roomconditioned at 25° C. and 50 RH% for 24 hours.

[0469] Hereinafter, Examples are illustrated in relation to the presentinvention I.

Examples I-1 to I-3

[0470] 60 kg of a sufficiently dried polybutylene terephthalate chipswere heated to 140° C. in a batch type tank type reaction vessel, andthere were supplied 42.6, 41.2, and 40.8 kg of ε-caprolactone heated to200° C., respectively, into the vessel. While agitating at 230° C. undera nitrogen gas atmosphere, a reaction was conducted, respectively. At aperiod at which average concentration of unreacted lactone intends tobecome 2.53, 1.19, and 0.79% by weight, respectively, pellet like resinswere taken out to measure an amount of the unreacted lactone and an acidvalue. The resins obtained were further placed under a reduced pressureat 120° C. in a pellet like to remove the unreacted lactone and tomeasure a melting point and an MI value. Results are collectively shownin Table I-1.

Comparative Example I-1

[0471] The same procedures were followed as in the Example I-1 exceptthat ε-caprolactone to be employed was changed to 40.4 kg and averageconcentration of unreacted lactone becomes 0.40% by weight to take out aresin and to analyze. Results are collectively shown in Table I-1.

Examples I-4 to I-6

[0472] A twin-screw extruder was equipped with a hopper and a screwstyle feeder at an upper portion. Likewise as in the Example I-1, asufficiently dried polybutylene terephthalate chips were filled in thehopper, and maintained under a nitrogen atmosphere. An equipment forcharging ε-caprolactone was equipped at a portion of the twin-screwextruder, and a tank which is maintained under a nitrogen atmosphere wasconnected through a pump. Operating conditions of apparatuses wereadjusted so that a temperature of a mixed liquid discharged from theextruder is maintained at 230° C.

[0473] Resins continuously discharged from the twin-screw extruder werecontinuously fed to a twin-screw continuous kneader having kneadingdiscs (KRC manufactured by Kurimoto Tekkosyo), and operating conditionsof apparatuses were adjusted so that a resin temperature is maintainedat 230° C.

[0474] Weight ratio of the polybutylene terephthalate resin with respectto ε-caprolactone was fixed at 42.6, 41.2, and 40.8, respectively, withrespect to 60 of the polybutylene terephthalate and, at a period atwhich average concentration of unreacted lactone becomes 2.53, 1.19, and0.79% by weight, respectively, pellet like resins were taken out tomeasure the amount of the unreacted lactone and an acid value. Theresins obtained were further placed at a reduced pressure and 120° C. toremove the unreacted lactones and to measure a melting point and an MIvalue.

[0475] Results are collectively shown in Table I-2.

Comparative Example I-2

[0476] The same procedures were followed as in the Example I-4 exceptthat the weight ratio of the polybutylene terephthalate resin withrespect to ε-caprolactone was fixed at 40.4 with respect to 60 of thepolybutylene terephthalate and average concentration of the unreactedlactone in, resins discharged is maintained 0.40% by weight to likewiseanalyze. Results are collectively shown in Table I-2.

Examples I-7 to I-9 and Comparative Example I-3

[0477] The same procedures were followed as in the Examples I-4 to I-6and Comparative Example I-2 except that temperature of respective resinsto be discharged is adjusted to 236° C. in a twin screw extrude and acontinuous kneader. Results are collectively shown in Table I-3. TABLEI-1 Comparative Example Example Example Example I-1 I-2 I-3 I-1 Reactiontime of period min 5.4 7.7 9.4 1.32 Concentration of Weight % 2.61 1.220.80 0.45 Unreacted lactone Acid value mgKOH/g 1.80 1.80 2.05 2.45 PeakTemperature in ° C. 204.4 203.7 202.3 198.3 Melting (Tm) Initiatingtemperature ° C. 189.0 187.9 185.8 180.7 Of melting (Tim) MI value g/10min 2.5 2.8 3.2 4.5

[0478] TABLE I-2 Comparative Example Example Example Example I-4 I-5 I-6I-2 Reaction time of Period min 4.9 6.7 8.1 1.12 Concentration of Weight% 2.60 1.21 0.81 0.43 Unreacted lactone Acid value mgKOH/g 1.75 1.751.85 2.25 Peak Temperature in ° C. 207.4 206.4 205.2 203.1 Melting (Tm)Initiation temperature ° C. 192.0 190.5 188.8 184.7 Of melting (Tim) MIvalue g/10 min 2.4 2.5 2.8 3.4

[0479] TABLE I-3 Comparative Example Example Example Example I-7 I-8 I-9I-3 Reaction time of Period min 4.0 5.5 6.8 9.8 Concentration of Weight% 2.60 1.21 0.81 0.43 Unreacted lactone Acid value mgKOH/g 1.85 1.902.00 2.55 Peak Temperature in ° C. 205.2 204.5 203.5 201.7 Melting (Tm)Initiating temperature ° C. 190.1 188.9 187.2 183.0 Of melting (Tim) MIvalue g/10 min 2.4 2.5 3.2 5.4

[0480] By the present invention I, in the case of obtaining a polyesterblock copolymer (P1) from a crystalline aromatic polyester and lactones,it was confirmed that there can be obtained the polyester blockcopolymer (P1) having a higher molecular weight which is excellentin-heat resistance and hydrolyzability by remaining a fixed amount ofunreacted lactones in the polyester block copolymer (P1).

[0481] Further, there was able to be confirmed an effect for elevating areaction rate of the crystalline aromatic polyester (A1) with lactones(B) by increasing an amount of the unreacted lactones.

[0482] Hereinafter, Examples are illustrated in relation to the presentinvention II.

Examples II-1 to II-3

[0483] 60 kg of a sufficiently dried polybutylene terephthalate chipswere heated to 140° C. in a batch type tank type reaction vessel, andthere were supplied 42.6, 41.2, and 40.8 kg of ε-caprolactone heated to200° C., respectively, into the vessel. While agitating at 230° C. undera nitrogen gas atmosphere, a reaction was conducted, respectively. At aperiod at which average concentration of unreacted lactone intends tobecome 2.53, 1.19, and 0.79% by weight, respectively, pellet like resinswere taken out to measure an amount of the unreacted lactone and an acidvalue. The pellet like resins obtained were further allowed to react ina flask equipped with agitating blades at 165° C. in a solid phase andcooled after 20 hours to measure a melting point and an MI value.Results are collectively shown in Table II-1.

Comparative Example II-1

[0484] The same procedures were followed as in the Example II-1 exceptthat ε-caprolactone to be employed was changed to 40.4 kg and averageconcentration of unreacted lactone becomes 0.40% by weight to take out aresin in a pellet state and to analyze. Results are collectively shownin Table II-1.

Examples II-4 to II-6

[0485] A twin-screw extruder was equipped with a hopper and a screwstyle feeder at an upper portion. Likewise as in the Example 1, asufficiently dried polybutylene terephthalate chips were filled in thehopper, and maintained under a nitrogen atmosphere. An equipment forcharging ε-caprolactone was equipped at a portion of the twin-screwextruder, and a tank which is maintained under a nitrogen atmosphere inwhich ε-caprolactone was filled was connected through a pump. Operatingconditions of apparatuses were adjusted so that a temperature of a mixedliquid discharged from the extruder is maintained at 230° C. Resinscontinuously discharged from the twin-screw extruder were continuouslyfed to a twin-screw continuous kneader having kneading discs (KRCmanufactured by Kurimoto Tekkosyo), and operating conditions ofapparatuses were adjusted so that a resin temperature is also maintainedat 230° C.

[0486] Weight ratio of the polybutylene terephthalate resin with respectto ε-caprolactone was fixed at 42.6, 41.2, and 40.8, respectively, withrespect to 60 of the polybutylene terephthalate and, at a period atwhich average concentration of unreacted lactone becomes 2.53, 1.19, and0.79% by weight, respectively, pellet like resins were taken out tomeasure the amount of the unreacted lactone and an acid value. Thepellet state resins obtained were further allowed to react in a solidphase at reduced pressure of 0.5 torr and 165° C. in a flask equippedwith agitating blades and cooled after 20 hours to remove the unreactedlactones and to measure a melting point and an MI value. Results arecollectively shown in Table II-2.

Comparative Example II-2

[0487] The same procedures were followed as in the Example II-4 exceptthat the weight ratio of the polybutylene terephthalate resin withrespect to ε-caprolactone was fixed at 40.4 with respect to 60 of thepolybutylene terephthalate and average concentration of the unreactedlactone in resins discharged is maintained 0.40% by weight to likewiseanalyze. Results are collectively shown in Table II-2.

Examples II-7 to II-9 and Comparative Example II-3

[0488] The same procedures were followed as in the Examples II-4 to II-6and Comparative Example II-2 except that respective temperatures ofresins to be discharged from the twin-screw extruder and the twin-screwcontinuous kneader were adjusted to 236° C. and the reactiontemperatures in a solid phase was adjusted to 170° C., and reaction timeof period in a solid phase was adjusted to 15 hours. Results arecollectively shown in Table II-3. TABLE II-1 Comparative Example ExampleExample Example II-1 II-2 II-3 II-1 Reaction time of min 4.2 5.8 7.21.18 Period at first step Concentration of Weight % 2.50 1.21 0.81 0.43Unreacted lactone Acid value mgKOH/g 2.75 2.80 3.00 3.45 PeakTemperature in ° C. 203.3 202.8 201.2 197.4 Melting (Tm) Initiationtemperature ° C. 187.7 186.6 184.4 179.2 Of melting (Tim) MI value g/10min 7.0 8.2 10.2 14.8

[0489] TABLE II-2 Comparative Example Example Example Example II-4 II-5II-6 II-2 Reaction time of min 3.4 4.5 5.5 8.5 Period at first stepConcentration of Weight % 2.53 1.20 0.80 0.41 Unreacted lactone Acidvalue mgKOH/g 2.55 2.60 2.85 3.30 Peak Temperature in ° C. 206.5 205.3204.4 202.3 Melting (Tm) Initiation temperature ° C. 190.7 189.2 187.3183.2 Of melting (Tim) MI value g/10 min 5.4 7.0 9.3 12.1

[0490] TABLE II-3 Comparative Example Example Example Example II-7 II-8II-9 II-3 Reaction time of min 2.6 3.4 4.1 6.6 Period at first stepConcentration of Weight % 2.55 1.22 0.81 0.40 Unreacted lactone Acidvalue mgKOH/g 2.55 2.65 2.90 3.50 Peak Temperature in ° C. 204.1 203.5202.3 200.9 Melting (Tm) Initiation temperature ° C. 188.9 187.3 185.8181.5 Of melting (Tim) MI value g/10 min 5.2 6.8 8.9 12.9

[0491] The polyester block copolymer having a high molecular weightobtained by the present invention II has a higher melting point thanthat of a copolymer obtained by conventional methods and, particularly,in which broadening of a low melting point portion can be reduced in amelting peak and, whereby, there was able to be obtained a polyesterblock copolymer which is excellent in heat resistance and moldingprocessability and has a higher viscosity and molecular weight.

[0492] Hereinafter, Examples are illustrated in relation to the presentinvention III.

Preparation Example III-1 Preparation of a Polyester Block Copolymer[TPEE (PA-1)]

[0493] 60 kg of a commercially supplied PBT ( ) and 40 kg ofε-caprolactone were fed in a reaction vessel, followed by allowing toreact in a melting state at 235° C. for 2 hours after purging nitrogen.After that, unreacted ε-caprolactone was removed at a reduced pressure,and a strand state resin was taken out of a valve set up at a bottom ofthe reaction vessel with a gear pump, followed by molding into pellets.In the resin obtained, an MI value was 15.2 g/10 minutes, tensilestrength was 290 kg/cm², and extension at break was 680%. A meltingpoint was 203.5° C., and an acid value was 1.5 mgKOH/g, and color huewas YI of 15.

Preparation Example III-2 Preparation of a Polyester Block Copolymer[TPEE (PA-2)]

[0494] There were heated 2390 parts of dimethylterephthalate, 1460 partsof a poly(tetramethylene)glycol having a number average molecular weightof 1400, and 1664 parts of 1,4-butanediol together with 0.04% (based ontotal of raw resin materials) of titanium tetrabutoxide which is acatalyst at 210° C. for 2 hours to distill off 95% of a theoreticalamount of methanol to an outside of a system.

[0495] Subsequently, temperature was raised to 245° C., and internalpressure of a system was reduced to not more than 0.2 mm Hg over 50minutes, and polymerization was conducted for 3 hours under theconditions. After that, a strand state resin was taken out of a valveset up at a bottom of the reaction vessel with a gear pump, followed bymolding into pellets. In the resin obtained, an MI value was 16.1 g/10minutes, tensile strength was 310 kg/cm², and extension at break was620%. A melting point was 210.4° C., and an acid value was 1.2 mgKOH/g,and color hue was YI of 21.

Examples III-1 to III-6

[0496] Into 100 parts by weight of a polyester block copolymer (PA-1) or(PA-2) obtained hereinabove, there were added after weighing compoundsselected from GPE, Kardula-E-10, TPP, sodium stearate, and Irganox 1010in the weight part described in Table III-1, respectively, followed bymixing in a drum tumbler at a room temperature for 30 minutes. Mixturewas melt-mixed using an extruder at 230° C. for a heating time of 1minute, extruded, and cut after cooled in water to pelletize. Pelletsobtained were fed into a tank type apparatus which can be heated andagitated, and can be pressure-reduced and purged by nitrogen, andpreheated at conditions of 100° C. and 100 torr for 3 hours. Further,the apparatus was purged by nitrogen and returned to an ordinarypressure, and a thermal treatment was conducted at 180° C. for a time ofperiod shown in Table III-1, respectively. After the treatment, theapparatus was cooled under nitrogen, and pellets were taken out tomeasure respective physical properties and analytical values.

[0497] Conditions and measurement results are shown in Table III-1.

[0498] In the Table, there are obtained resins, in which a decline ofcolor hue and viscosity is low, and which has excellent physicalproperties, and in which an acid value can be reduced by a small amountof the epoxy compounds. Further, volatile components in melt-mixing wereless in all Examples compared to the Comparative Examples.

Comparative Examples III-1 to III-8

[0499] Into 100 parts by weight of a polyester block copolymer (PA-1) or(PA-2), there were added after weighing compounds selected from GPE,Kardular E-10, TPP, sodium stearate, and Irganox 1010 in the weight partdescribed in Table III-2, respectively, followed by mixing in a drumtumbler at a room temperature for 30 minutes.

[0500] Mixture was melt-mixed while controlling a feeding amount usingan extruder at a temperature shown in Table III-2 extruded, and cutafter cooled, respectively, in water to pelletize.

[0501] Respective physical properties and analytical values weremeasured in relation to the pellets obtained. Conditions and measurementresults are shown in Table III-2. From the Table, it was confirmed thata large amount of the epoxy compounds are required in order tosufficiently lower an acid value, and it is supposed that there becomeworse physical properties such as color hue and viscosity.

Examples III-7 to III-10

[0502] Into 100 parts by weight of a polyester block copolymer (PA-1),there were added after weighing compounds selected from GPE, KardularE-10, TPP, sodium stearate, and Irganox 1010 in the weight partdescribed in Table III-3, respectively, followed by mixing in a drumtumbler at a room temperature for 30 minutes. Mixture was melt-mixedusing an extruder at 230° C. for a heating time of 1 minute, extruded,and cut after cooled in water to pelletize.

[0503] Pellets obtained were fed into a tank type apparatus which can beheated and agitated, and can be pressure-reduced and purged by nitrogen,and preheated at conditions of 100° C. and 100 torr for 2 hours.Further, the apparatus was purged by nitrogen and returned to anordinary pressure, and a thermal treatment was conducted at 180° C. fora time of period shown in Table III-3, respectively.

[0504] After the treatment, the apparatus was cooled under nitrogen, andpellets were taken out to measure respective physical properties andanalytical values. Conditions and measurement results are shown in TableIII-3. In the Table, there are obtained resins and, in which an acidvalue can be reduced by a small amount of the epoxy compounds and, inwhich viscosity is sufficiently elevated and an elevation of viscosityby remelting is less, and which has excellent color hue and physicalproperties.

Comparative Examples III-9 to III-13

[0505] Into 100 parts by weight of a polyester block copolymer (PA-1),there were weighed compounds selected from GPE, Kardular E-10, TPP,sodium stearate, and Irganox 1010 in the weight part described in TableIII-4, respectively, followed by mixing in a drum tumbler at a roomtemperature for 30 minutes. Mixture was melt-mixed while controlling afeeding amount using an extruder at a temperature of 260° C. for 5minute, extruded, and cut after cooled in water to pelletize. Respectivephysical properties and analytical values were measured in relation tothe pellets obtained. Conditions and measurement results are shown inTable III-4. From the Table, it was confirmed that a large amount of theepoxy compounds are required in order to sufficiently lower an acidvalue, and an elevation of viscosity is not sufficiently caused, and anelevation of viscosity by reheating is large.

Example III-11

[0506] Into 100 parts by weight of a polyester block copolymer (PA-1),there were weighed compounds selected from GPE, BFDGE, TPP, and Irganox1010 in the weight part described in Table III-3, respectively, followedby mixing in a drum tumbler at a room temperature for 30 minutes.Mixture was melt-mixed using an extruder at 230° C. for a heating timeof 1 minute, extruded, and cut after cooled in water to pelletize.Pellets obtained were fed into a tank type apparatus which can be heatedand agitated, and can be pressure-reduced and purged by nitrogen, andelevated to 180° C. at an ordinary pressure, and a thermal treatment wasconducted for 10 hours. After cooled under nitrogen, and pellets weretaken out to measure respective physical properties and analyticalvalues.

[0507] Conditions and measurement results are shown in Table III-3.TABLE III-1 Example Example Example Example Example Example III-1 III-2III-3 III-4 III-5 III-6 TPEE Kind PA-1 PA-1 PA-1 PA-1 PA-1 PA-2 GPE PBW0.9 0.9 0.9 CE-10*¹ PBW 1.5 1.5 1.5 TPP PBW 0.1 0.1 St-Na*² PBW 0.1 0.10.1 0.1 IR*³ PBW 0.5 0.5 Preheating Temperature 100° C. 100° C. 100° C.100° C. 100° C. 100° C. Torr 100 Torr, 100 Torr, 100 Torr, 100 Torr, 100Torr, 100 Torr, Time 3 Hr 3 Hr 3 Hr 3 Hr 3 Hr 3 Hr Heating temperature °C. 180 180 180 180 180 180 Heating time hour 4 8 6 6 6 6 Acid valuemgKOH/g 0.15 0.05 0.08 0.05 0.07 0.08 Color hue (YI) 19 22 22 21 23 28MI value g/10 min 15.8 16.0 15.8 15.8 16.3 17.3 Melting point ° C. 203.3203.2 203.5 203.2 203.1 209.3 Tensile strength at kg/cm² 340 340 350 340330 330 break Tensile extension at % 680 690 700 690 700 700 breakHidrolysis resistance % 90 100 100 100 100 100 Thermal decomposition %80 90 90 90 100 100

[0508] TABLE III-2 Comparative Comparative Comparative ComparativeComparative Comparative Comparative Comparative Example Example ExampleExample Example Example Example Example III-1 III-2 III-3 III-4 III-5III-6 III-7 III-8 TPEE Kind PA-1 PA-1 PA-1 PA-1 PA-1 PA-1 PA-1 PA-2 GPEPart by 0.9 0.9 1.8 1.8 weight CE-10*¹ Part by 3.0 3.0 3.0 3.0 weightTPP Part by 0.1 0.1 0.1 0.1 0.1 weight St-Na*² Part by 0.1 0.1 0.1weight IR*³ Part by 0.5 0.5 weight Melt mixing ° C. 240 260 260 260 260260 260 260 temperature Melt mixing time of Minute 1.0 2.5 2.5 5.0 5.05.0 5.0 5.0 period Thermal treatment None None None None None None NoneNone None Acid value mgKOH/g 1.10 0.78 0.52 0.32 0.22 0.11 0.08 0.12Color hue (Y 20 26 25 29 28 30 35 41 I) MI value g/10 min 15.4 16.0 16.817.2 17.1 16.7 16.3 17.1 Melting point ° C. 203.4 203.1 202.0 199.2198.0 197.5 197.2 200.1 Tensile strength at kg/cm² 340 350 330 300 320330 320 350 break Tensile extension at % 680 690 670 620 640 640 640 610break Hydrolysis resistance % 0 0 20 40 50 100 90 90 Heat decomposition% 50 50 60 70 70 70 90 80 resistance

[0509] TABLE III-3 Example Example Example Example Example III-7 III-8III-9 III-10 III-11 TPEE Kind PA-1 PA-1 PA-1 PA-1 PA-1 GPE Part byweight 0.45 0.45 0.45 0.15 0.45 BFDGE*⁴ Part by weight 0.47 0.47 0.620.47 CHDDG*⁵ Part by weight 0.43 TPP Part by weight 0.1 0.1 0.1 0.1 0.1St-Na*² Part by weight IR*³ Part by weight 0.5 0.5 0.5 0.5 PreheatingTemperature 100° C. 100° C. 100° C. 100° C. No preheating Torr 100 Torr,100 Torr, 100 Torr, 100 Torr, Time of period 2 Hr 2 Hr 2 Hr 2 Hr Thermaltreatment ° C. 180 180 180 180 180 temperature Thermal treatment Time ofperiod 10 10 10 10 10 time of period Acid value mgKOH/g 0.15 0.10 0.050.06 0.10 Color hue (YI) 20 23 24 23 25 MI value g/10 min 6.8 5.4 5.81.8 6.5 Melting point ° C. 203.3 203.2 203.5 203.2 203.1 Tensilestrength at break kg/cm² 360 370 350 380 350 Tensile extension at break% 720 710 700 680 720 Hydrolysis resistance % 90 100 100 100 100 Heatdecomposition % 90 100 100 100 100 resistance Melt viscosity stability0.95 0.92 0.98 1.03 1.05

[0510] TABLE III-4 Comparative Comparative Comparative ComparativeComparative Example III-9 Example III-10 Example III-11 Example III-12Example III-12 TPEE Kind PA-1 PA-1 PA-1 PA-1 PA-1 GPE Part by weight0.45 0.90 1.35 1.35 1.35 BFDGE*⁴ Part by weight 0.47 0.94 0.47 0.47 0.47TPP Part by weight 0.1 0.1 0.1 0.1 0.1 IR*³ Part by weight 0.5 Meltmixing temperature ° C. 260 260 260 260 260 Melt mixing time of periodMinute 5.0 5.0 5.0 5.0 5.0 Thermal treatment None None None None NoneNone time of period Acid value mgKOH/g 0.53 0.25 0.15 0.10 0.17 Colorhue (YI) 27 26 29 28 32 MI value g/10 min 14.9 10.1 14.6 13.3 15.2Melting point ° C. 197.6 195.2 198.2 198.4 198.2 Tensile strength atbreak kg/cm² 310 280 300 340 330 Tensile extension at break % 680 290710 700 700 Hydrolysis resistance % 20 60 90 100 90 Heat decomposition %60 80 90 90 100 resistance Melt viscosity stability 0.47 Gelation 0.650.69 0.73

[0511] In the present invention III, there can be controlled a reactionratio of the epoxy compound (C) employed by thermally treating thepolyester block copolymer composition (Q) in a solid phase, and an acidvalue can be particularly suppressed in a low level. Whereby, there canbe improved heat resistance and hydrolysis resistance, and there can beprovided the composition (R) having a melt viscosity stability bydecreasing residual epoxy compounds, and which has a more excellentcolor hue compared to a product obtained by conventional methods for thepreparation.

[0512] Hereinafter, Examples are illustrated in relation to the presentinvention IV.

Reference Example IV-1 Preparation of a Polyester Block copolymer (P₁′)

[0513] 80 parts of a commercially supplied PBT (A₁) and 20 parts ofε-caprolactone (B₁) were fed into the reaction vessel, and a reactionwas conducted at 235° C. for 1 hour while agitating.

[0514] Subsequently, pressure was reduced from an ordinary pressure tonot more than 1 torr over 1 hour while maintaining the temperature, andresidual ε-caprolactone in a system was removed while maintaining areduced pressure state for further 1 hour.

[0515] In the polyester block copolymer (P₁′) obtained, a melting pointwas 185° C., and MI was 11 g/10 minutes.

Reference Example IV-2 Preparation of a Polyester Block Copolymer (P₂′)

[0516] 85 parts of a commercially supplied PBT (A₂) and 15 parts ofε-caprolactone (B₁) were fed into the vessel, and a reaction wasconducted at 235° C. for 1 hour while agitating.

[0517] Subsequently, pressure was reduced from an ordinary pressure tonot more than 1 torr over 1 hour while maintaining the temperature, andresidual ε-caprolactone in a system was removed while maintaining areduced pressure state for further 1 hour.

[0518] In the polyester block copolymer (P2′) obtained, melting pointwas 174° C., and MI was 12 g/10 minutes.

Examples IV-1 to IV-24

[0519] Polyester block copolymer composition is a compound in which anepoxy compound (C₁ or C₂) having one or more functionalities, an oxalicacid derivative (D₁), salicylic acid derivatives (D₂ and D₃), ahydrazide derivative (D₄), and a variety of stabilizers (E₁ and E₂) aremixed with the polyester block copolymer (P₁′ or P₂′) prepared in theReference Examples IV-1 and IV-2, and heated and kneaded by an extruder.Formulation amount is shown in Table IV-1.

[0520] Test pieces were prepared using the polyester block copolymercomposition.

[0521] A copper foil having width of 5 mm was spirally wound at a pitchof 5 mm interval between marked lines in the test samples.

[0522] Subsequently, the test pieces around which the copper foil iswound were put between PVC sheets having 30 mm (length)×30 mm (width)×1mm (thickness) and, further, the PVC sheets in which the test pieces areput between were put between SUS 304-made metal plates having 35 mm(length)×35 mm (width)×3 mm (thickness) to prepare a composite layer.The weight of 5 kgf was placed on the composite layer, followed byplacing in an oven set up at 140° C.

[0523] Tensile extension at break was measured in relation to the testpieces placed in the oven.

[0524] Results are shown in Table IV-3. A higher change with a lapse oftime in the tensile extension at break shows a more progresseddeterioration.

Comparative Examples IV-1 to IV-7

[0525] Likewise as in the Examples IV-1 to IV-24, a polyester blockcopolymer composition is a compound in which a variety of additives aremixed with the polyester block copolymer (P₁′ or P₂′) prepared in theReference Examples IV-1 and IV-2, and heated and kneaded by an extruder.Formulation amount is shown in Table IV-1.

[0526] In relation to the polyester block copolymer composition, testsaccording to the Example IV-1 were conducted. Results in measurement areshown in Table IV-3.

Comparative Examples IV-8 to IV-13

[0527] A polyamide resin having a relative viscosity of 1.80 and amelting point of 178° C. was obtained by adding dodecanoic diacid inpolymerization of a Nylon 12 of Daicel Huels, Ltd. It is to be notedthat the relative viscosity in the polyamide resin was obtained bymeasurement of a solution viscosity in which a 0.5%-metacresol solutionaccording to DIN 53727.

[0528] A variety of additives were formulated in the polyamide resin asshown in Table IV-2, followed by compounding to prepare a polyamideresin composition by an extruder.

[0529] In relation to the polyamide resin composition, tests accordingto the Example IV-1 were conducted. Results in measurement are shown inTable IV-3.

[0530] It is to be noted that symbols in the Table IV-1 and the TableIV-2 are as follows.

[0531] C₁ Monoglycidylester (Trade name: Kardula E10 manufactured byShell Japan)

[0532] C₂ Diglycidylester (Trade name: Epomic R540 manufactured byMitsui Kagaklu)

[0533] D₁ Oxalic acid derivative: bisbenzylidenehydrazide oxalate

[0534] D₂ Salicylic acid derivative 1:3-(salicyloyl)amino-1,2,4-triazole

[0535] D₃ Salicylic acid derivative 2: decanedicarboxylic aciddisalicyloyl hydrazide

[0536] D₄ Hydrazide derivative:N,N′-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine

[0537] E₁ Stabilizer 1:Tetrakis[methylene-3-(3′,5′-di-t-butyl-4-hydroxyphenyl)propionate]methane

[0538] E₂ Stabilizer 2: Organic composite phosphite (Trade name:Advastab (manufactured by Katsuta Kako)) TABLE IV-1 Polyester PolyesterSuccinic Salicylic Salicylic block block Epoxy Epoxy acid acid acidHydrazid copolymer copolymer compound compound derivative derivativederivative derivative Stabilyzer Stabilyzer P₁′ P₂′ C₁ C₂ D₁ D₂ D₃ D₄ E₁E₂ PBW PBW PBW PBW PBW PBW PBW PBW PBW PBW Example IV-1 100 0.6 0.8 0.3Example IV-2 100 1.0 1.0 0.5 Example IV-3 100 0.6 0.8 0.5 0.5 0.5Example IV-4 100 0.6 0.8 0.3 Example IV-5 100 1.0 1.0 0.5 Example IV-6100 0.6 0.8 0.5 0.5 0.5 Example IV-7 100 0.6 0.8 0.3 Example IV-8 1001.0 1.0 0.5 Example IV-9 100 0.6 0.8 0.5 0.5 0.5 Example IV-10 100 0.60.8 0.3 Example IV-11 100 1.0 1.0 0.5 Example IV-12 100 0.6 0.8 0.5 0.50.5 Example IV-13 100 0.6 0.8 0.3 Example IV-14 100 1.0 1.0 0.5 ExampleIV-15 100 0.6 0.8 0.5 0.5 0.5 Example IV-16 100 0.6 0.8 0.3 ExampleIV-17 100 1.0 1.0 0.5 Example IV-18 100 0.6 0.8 0.5 0.5 0.5 ExampleIV-19 100 0.6 0.8 0.3 Example IV-20 100 1.0 1.0 0.5 Example IV-21 1000.6 0.8 0.5 0.5 0.5 Example IV-22 100 0.6 0.8 0.3 Example IV-3 100 1.01.0 0.5 Example IV-4 100 0.6 0.8 0.5 0.5 0.5 C. Ex. IV-1 100 C. Ex. IV-2100 0.5 C. Ex. IV-3 100 0.5 0.5 C. Ex. IV-4 100 0.6 0.8 C. Ex. IV-5 1000.6 0.6 0.5 C. Ex. IV-6 100 0.5 C. Ex. IV-7 100 0.5

[0539] TABLE IV-2 Salicylic Salicylic Salicylic Poly acid acid acidHydrazide amide Deriv. Deriv. Deriv. Deriv. Stabilizer Stabilizer resinD₁ D₂ D₃ D₄ E₁ E₂ PBW PBW PBW PBW PBW PBW PBW C. Exam. IV-8 100 C. Exam.IV-9 100 0.5 0.5 C. Exam. IV-10 100 0.5 0.5 0.5 C. Exam. IV-11 100 0.50.5 0.5 C. Exam. IV-12 100 0.5 0.5 0.5 C. Exam. IV-13 100 0.5 0.5 0.5

[0540] TABLE IV-3 Tensile strength at break (%) Placed days 0 5 7 10 1417 20 23 27 30 Example IV-1 485 480 485 460 435 410 390 325 190 50Example IV-2 470 480 480 470 450 390 385 310 160 45 Example IV-3 465 475470 470 465 440 415 370 305 240 Example IV-4 420 435 420 410 400 360 290210 80 25 Example IV-5 415 420 420 395 400 350 265 240 110 25 ExampleIV-6 420 425 425 420 405 390 325 270 200 60 Example IV-7 480 475 470 450435 400 375 305 175 45 Example IV-8 465 460 465 440 435 410 390 290 21590 Example IV-9 460 475 460 445 450 435 405 385 325 215 Example IV-10420 420 420 390 380 360 300 240 120 40 Example IV-11 410 430 400 400 365370 320 245 135 0 Example IV-12 420 425 420 420 405 390 370 345 290 175Example IV-13 490 470 475 470 465 410 355 280 245 80 Example IV-14 480480 470 455 465 430 400 265 205 110 Example IV-15 470 485 480 460 455450 425 410 385 310 Example IV-16 430 415 410 405 400 375 340 295 200 95Example IV-17 440 430 420 400 395 375 350 305 190 100 Example IV-18 435430 420 420 420 405 395 345 300 190 Example IV-19 490 450 440 420 415395 335 245 120 25 Example IV-20 460 440 435 440 440 420 370 275 114.525 Example IV-21 460 465 460 445 450 430 405 370 360 190 Example IV-22420 420 425 400 390 365 335 275 180 100 Example IV-23 430 430 420 415410 400 385 290 160 40 Example IV-25 420 420 410 410 405 400 390 345 275170 C. Ex. IV-1 480 300 185 0 0 0 0 0 0 0 C. Ex. IV-2 480 450 425 380375 300 260 125 0 0 C. Ex. IV-3 475 460 430 400 360 280 225 95 0 0 C.Ex. IV-4 490 470 460 390 245 90 0 0 0 0 C. Ex. IV-5 485 490 440 410 380210 75 0 0 0 C. Ex. IV-6 480 400 325 220 60 0 0 0 0 0 C. Ex. IV-7 475415 330 220 135 45 0 0 0 0 C. Ex. IV-8 360 50 0 0 0 0 0 0 0 0 C. Ex.IV-9 350 170 45 0 0 0 0 0 0 0 C. Ex. IV-10 355 350 300 295 290 160 0 0 00 C. Ex. IV-11 360 320 280 250 0 0 0 0 0 0 C. Ex. IV-12 330 315 300 315295 250 0 0 0 0 C. Ex. IV-13 320 325 315 300 220 65 0 0 0 0

[0541] The polyester block copolymer composition of the presentinvention IV has an excellent heat resistance in contact with a metaland a PVC and, it is preferred as a heat sensitive body to be employedfor a heater code in an electric blanket and electric carpet, and it canbe also employed for a long time of period as a heat sensitive body evenin direct contact with a metal-made short code or a heating wire and aPVC which is an outer cover.

[0542] Hereinafter, Examples are illustrated in relation to the presentinvention V.

Comparative Example V-1

[0543] 60 parts of a PBT (A1) and 40 parts of ε-caprolactone were fedinto a reaction vessel, and a reaction was conducted at 235° C. for 1hour while agitating. Subsequently, pressure was reduced from anordinary pressure to not more than 1 torr over 1 hour while maintainingthe temperature, and residual ε-caprolactone in a system was removedwhile maintaining a reduced pressure state for further 1 hour.

[0544] In the polyester block copolymer obtained, a melting point was205° C., and MI was 11 g/10 minutes. It is to be noted that the modulusof strain hardening was not observed.

Comparative Example V-2

[0545] 30 parts by weight of Celloxide 2021P and 1 part by weight of2-ethyl-4-methylimidazole were formulated with 100 parts of a polyesterblock copolymer obtained in the Comparative Example V-1, followed bycompounding to prepare a composition by a twin screw extruder.

[0546] In the composition obtained, an MI was 2 g/10 minutes, and themodulus of strain hardening was not observed.

Reference Example V-1

[0547] 60 parts of a PBT (A1), 40 parts of ε-caprolactone, and 5% by mol(0.0103 part by weight) of trimethylolpropane were fed into the reactionvessel, and a reaction was conducted at 235° C. for 1 hour whileagitating. Subsequently, pressure was decreased from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour to obtain apolyester block copolymer (PA).

[0548] In the polyester block copolymer (PA) obtained, a melting pointwas 194° C., and MI was 2 g/10 minutes, and the modulus of strainhardening was observed.

Reference Example V-2

[0549] 60 parts of a PBT (A₁), 40 parts of ε-caprolactone, and 2.5% bymol (0.0052 part by weight) of trimethylolpropane were fed into thereaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was decreased from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour to obtain apolyester block copolymer (PB).

[0550] In the polyester block copolymer (PB) obtained, a melting pointwas 196° C., and MI was 1 g110 minutes, and the modulus of strainhardening was slightly observed.

Reference Example V-3

[0551] 60 parts of a PBT (A1), 40 parts of ε-caprolactone, and 0.1% bymol (0.206×10⁻³ part by weight) of trimethylolpropane were fed into areaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was reduced from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour to obtain apolyester block copolymer (PC).

[0552] In the polyester block copolymer (PC) obtained, a melting pointwas 194° C., and MI was 5 g/10 minutes, and the modulus of strainhardening was slightly observed.

Examples V-1 to V-11

[0553] A polyester block copolymer composition was prepared byformulating and compounding through heating and kneading an epoxycompound having one or more functionalities and a carbodiimide compoundby an extruder with the polyester block copolymers prepared in theReference Examples V-1 to V-3 at a ratio shown in Table V-1 to measurethe modulus of strain hardening. Results are shown in Table V-1.

[0554] Further, test pieces and conditioned test pieces were preparedusing the polyester block copolymer compositions, and tensile extensionat break was measured in relation to the conditioned test pieces.Results are shown in Table V-2.

[0555] A higher change ratio of the tensile extension at break with alapse of time shows a more progressed deterioration.

Comparative Example V-3

[0556] 60 parts of a PBT (A₁), 40 parts of ε-caprolactone, and 150% bymol (0.309 parts by weight) of trimethylolpropane were fed into areaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was reduced from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour to obtain apolyester block copolymer.

[0557] In the polyester block copolymer obtained, a melting point was179° C. which was fairly lowered, and MI was 2 g/10 minutes, and themodulus of strain hardening was observed.

Comparative Examples V-4 to V-6

[0558] Likewise as in the Examples V-1 to V-11, a polyester blockcopolymer composition was prepared by formulating and compoundingthrough heating and kneading a variety of additives by a twin-screwextruder with the polyester block copolymer prepared in the ReferenceExamples V-1 to V-3. Formulation amount is shown in Table V-1. Inrelation to the polyester block copolymer composition, tests wereconducted according to the Examples V-1 to V-11. Results in measurementare shown in Table V-2. TABLE V-1 Polyester Polyester Polyester blockblock block Epoxy Epoxy Carbodiimide Modulus copolymer copolymercopolymer compound compound compound Stabilizer Stabilizer of (PA) (PB)(PC) C1 C2 E1 F1 F2 Strain- PBW PBW PBW PBW PBW PBW PBW PBW hardeningExam. V-1 100 0.6 0.8 ⊚ Exam. V-2 100 1.0 1.0 ⊚ Exam. V-3 100 0.6 0.80.5 ⊚ Exam. V-5 100 0.6 0.8 ⊚ Exam. V-6 100 1.0 1.0 ⊚ Exam. V-7 100 0.60.8 0.5 ⊚ Exam. V-8 100 0.6 0.8 0.5 0.5 ⊚ Exam. V-9 100 0.6 0.8 0.5 ◯Exam. V-10 100 1.0 1.0 0.5 ◯ Exam. V-11 100 0.6 0.8 0.5 0.5 0.5 ◯ C. Ex.V-4 100 5.0 5.0 Gel C. Ex. V-5 100 5.0 5.0 Gel C. Ex. V-6 100 0.5 0.10.5 0.5 X

[0559] TABLE V-2 Tensile extension at break (%) Placed days 0 5 7 10 1417 20 23 27 30 Example V-1 420 435 420 410 400 360 290 210 80 25 ExampleV-2 415 420 420 395 400 350 265 240 110 25 Example V-3 480 475 470 450435 400 375 305 175 45 Example V-4 420 425 425 420 405 390 325 270 20060 Example V-5 470 480 480 470 450 390 385 310 160 45 Example V-6 485480 485 460 435 410 390 325 190 50 Example V-7 460 475 460 445 450 435405 385 325 215 Example V-8 465 460 465 440 435 410 390 360 330 260Example V-9 490 495 490 490 485 460 370 220 160 55 Example V-10 495 510515 515 510 480 440 400 350 250 Example V-11 480 485 480 480 475 460 420400 370 340 C. Example V-1 480 300 185 0 0 0 0 0 0 0 C. Example V-2 480475 475 460 435 400 360 305 190 60 C. Example V-3 475 350 200 0 0 0 0 00 0 C. Example V-6 460 470 460 440 430 400 370 330 290 200

[0560] It is large in dependence upon extension rate, and provides amolded article having uniform thickness in blow molding and, further, ithas a characteristic of exceedingly less flashes in molding. Moreover, amolded article obtained from a composition is very excellent in heatresistance in addition to properties inherently possessed by a polyesterblock copolymer. It does not cause a thermal deterioration even beingemployed for a use exposed to a high temperature for a long time ofperiod, and it provides a molded article having very excellent physicalproperties.

[0561] Hereinafter, Examples are illustrated in relation to the presentinvention VI.

Reference Example VI-1 Preparation of a Polyester Block Copolymer (P-A)

[0562] 60 parts of a PBT (A₁), 40 parts of ε-caprolactone, and 150% bymol of 2,4-dihydroxy benzoate based on 100% by mol of polybutylenephthalate were fed into a reaction vessel, and a reaction was conductedat 235° C. for 1 hour while agitating.

[0563] Subsequently, pressure was reduced from an ordinary pressure tonot more than 1 torr over 1 hour while maintaining the temperature, andresidual ε-caprolactone in a system was removed while maintaining areduced pressure state for further 1 hour. In the polyester blockcopolymer obtained, a melting point was 190° C., and MI was 2 g/10minutes. Further, the modulus of strain hardening was observed. Thepolyester block copolymer was designated as Copolymer (P-A).

Reference Example VI-2 Preparation of a Polyester Block Copolymer (P-B)

[0564] 60 parts of a PBT (A1), 40 parts of ε-caprolactone, and 50% bymol of 2,4-dihydroxy benzoate based on 100% by mol of a polybutylenephthalate were fed into a reaction vessel, and a reaction was conductedat 235° C. for 1 hour while agitating.

[0565] Subsequently, pressure was reduced from an ordinary pressure tonot more than 1 torr over 1 hour while maintaining the temperature, andresidual ε-caprolactone in a system was removed while maintaining areduced pressure state for further 1 hour. In the polyester blockcopolymer obtained, a melting point was 199° C., and MI was 4 g/10minutes. Further, the modulus of strain hardening was observed. Thepolyester block copolymer was designated as Copolymer (P-B).

Reference Example VI-3 Preparation of a Polyester Block Copolymer (P-C)

[0566] 60 parts of a PBT (A1), 40 parts of ε-caprolactone, and 0.1% bymol of 2,4-dihydroxy benzoate based on 100% by mol of polybutylenephthalate were fed into a reaction vessel, and a reaction was conductedat 235° C. for 1 hour while agitating.

[0567] Subsequently, pressure was decreased from an ordinary pressure tonot more than 1 torr over 1 hour while maintaining the temperature, andresidual ε-caprolactone in a system was removed while maintaining areduced pressure state for further 1 hour. In the polyester blockcopolymer obtained, a melting point was 205° C., and MI was 5 g/10minutes. Further, the modulus of strain hardening was observed. Thepolyester block copolymer was designated as Copolymer (P-C).

Examples VI-1 to VI-11

[0568] Polyester block copolymer composition was prepared by formulatingand compounding through heating and kneading an epoxy compound havingone or more functionalities and a carbodiimide compound by an extruderwith the polyester block copolymers (P-A), (P-B), and (P-C) prepared inthe Reference Examples VI-1 to VI-3.

[0569] Formulating amount and the presence or absence of the modulus ofstrain hardening are shown in Table VI-1.

[0570] Further, test pieces and conditioned test pieces were preparedusing the polyester block copolymer compositions, and tensile extensionat break was measured in relation to the conditioned test pieces.Results are shown in Table VI-2. A higher change ratio of the tensileextension at break with a lapse of time shows a more progresseddeterioration.

Comparative Example VI-1

[0571] 60 parts of a PBT (A1) and 40 parts of ε-caprolactone were fedinto a reaction vessel, and a reaction was conducted at 235° C. for 1hour while agitating. Subsequently, pressure was decreased from anordinary pressure to not more than 1 torr over 1 hour while maintainingthe temperature, and residual ε-caprolactone in a system was removedwhile maintaining a reduced pressure state for further 1 hour. In thepolyester block copolymer obtained, a melting point was 205° C., and MIwas 11 g/10 minutes. The modulus of strain hardening was not observed.

Comparative Example VI-2

[0572] 30 parts by weight of Celloxide 2021P and 1 part by weight of2-ethyl-4-methylimidazole were formulated with 100 parts of a polyesterblock copolymer obtained in the Comparative Example VI-1, followed bycompounding to prepare a composition by an extruder. In the compositionobtained, an MI was 2 g/10 minutes, and the modulus of strain hardeningwas not observed.

Comparative Example VI-3

[0573] 60 parts of a PBT (A₁), 40 parts of ε-caprolactone, and 300% bymol of 2,4-dihydroxy benzoate based on 100% by mol of a polybutylenephthalate were fed into a reaction vessel, and a reaction was conductedat 235° C. for 1 hour while agitating.

[0574] Subsequently, pressure was decreased from an ordinary pressure tonot more than 1 torr over 1 hour while maintaining the temperature, andresidual ε-caprolactone in a system was removed while maintaining areduced pressure state for further 1 hour. In the polyester blockcopolymer obtained, a melting point was 179° C. which is fairly lowered,and MI was 1 g/10 minutes. The modulus of strain hardening was observed.

Comparative Examples VI-4 to VI-6

[0575] Likewise as in the Examples VI-1 to VI-11, polyester blockcopolymer composition was prepared by formulating and compoundingthrough heating and kneading a variety of additives by an extruder withthe polyester block copolymers (P-A), (P-B), and (P-C) prepared in theReference Examples VI-1 to VI-3. Formulating amount is shown in TableVI-1. In relation to the polyester block copolymer compositions, testswere conducted according to the Examples VI-1 to VI-11. Results inmeasurement are shown in Table V-2. TABLE VI-1 Polyester PolyesterPolyester block block block Epoxy Epoxy Carbodi- Modulus copolymercopolymer copolymer Compound Compound imide Stabilizer Stabilizer of(P-A) (P-B) (P-C) 1¹⁾ 2²⁾ Compound³⁾ 1⁴⁾ 2⁵⁾ Strain- PBW PBW PBW PBW PBWPBW PBW PBW hardening⁶⁾ Exam. VI-1 100 0.6 0.8 ⊚ Exam. VI-2 100 1.0 1.0⊚ Exam. VI-3 100 0.6 0.8 0.5 ⊚ Exam. VI-4 100 0.6 0.8 0.5 0.5 ⊚ Exam.VI-5 100 0.6 0.8 ⊚ Exam. VI-6 100 1.0 1.0 ⊚ Exam. VI-7 100 0.6 0.8 0.5 ⊚Exam. VI-8 100 0.6 0.8 0.5 0.5 ⊚ Exam. VI-9 100 0.6 0.8 0.5 ◯ Exam.VI-10 100 1.0 1.0 0.5 ◯ Exam. VI-11 100 0.6 0.8 0.5 0.5 0.5 ◯ C. Ex.VI-4 100 5.0 5.0 Gel C. Ex. VI-5 100 5.0 5.0 Gel C. Ex. VI-6 100 0 0 0.50.5 0.5 X

[0576] TABLE VI-2 Tensile extention at break (%) Placed days 0 5 7 10 1417 20 23 27 30 Example VI-1 440 440 430 420 400 360 290 210 80 30Example VI-2 415 420 420 395 380 360 310 240 110 30 Example VI-3 450 470470 450 435 400 375 305 175 45 Example VI-4 420 425 425 420 405 390 370330 270 205 Example VI-5 480 480 480 470 450 390 385 310 160 45 ExampleVI-6 460 470 470 460 435 410 390 325 190 50 Example VI-7 460 475 460 450450 435 405 385 310 205 Example VI-8 430 445 450 440 435 410 380 350 310260 Example VI-9 490 495 490 490 485 460 370 220 160 60 Exam. VI-10 495510 515 515 510 470 430 370 300 220 Exam. VI-11 480 485 480 480 475 450410 365 310 250 C. Exam. VI-1 480 300 185 0 0 0 0 0 0 0 C. Exam. VI-2480 475 475 460 435 400 360 305 190 60 C. Exam. VI-3 475 350 200 0 0 0 00 0 0 C. Exam. VI-6 460 470 460 440 430 400 370 330 290 200

[0577] Since the composition by the present invention VI has the modulusof strain hardening, it is supposed that there can be obtained a moldedarticle having uniform thickness in blow molding and, moreover, sincethe molded article has a low change ratio of the tensile extension atbreak with a lapse of time, there can be obtained a polyester blockcopolymer composition having a lower deterioration with a lapse of time.A molded article obtained using the composition is very excellent inheat resistance in addition to properties inherently possessed by apolyester block copolymer, and the molded article does not cause athermal deterioration even being employed for a use exposed to a hightemperature for a long time of period.

[0578] Hereinafter, Examples are illustrated in relation to the presentinvention VII.

Preparation Example VII-1

[0579] 60 parts of a polybutylene terephthalate (A1), 40 parts ofε-caprolactone, and 150% by mol of trimethylolpropane were fed into areaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was reduced from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour. In thepolyester block copolymer obtained, a melting point was 190° C., and anumber average molecular weight was 56000.

[0580] The copolymer is designated as Polyester block copolymer (P-A).

Preparation Example VII-2

[0581] 60 parts of a polybutylene terephthalate (A1), 40 parts ofε-caprolactone, and 50% by mol of trimethylolpropane were fed into areaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was decreased from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour. In thepolyester block copolymer obtained, a melting point was 199° C., and anumber average molecular weight was 61000. The copolymer is designatedas Polyester block copolymer (P-B).

Preparation Example VII-3

[0582] 60 parts of a polybutylene terephthalate (A₁), 40 parts ofε-caprolactone, and 0.1% by mol of trimethylolpropane were fed into areaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was reduced from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour. In thepolyester block copolymer obtained, a melting point was 205° C., and anumber average molecular weight was 71200. The copolymer is designatedas Polyester block copolymer (P-C).

Preparation Example VII-4

[0583] 60 parts of a polybutylene terephthalate (A₁), 40 parts ofε-caprolactone, and 150% by mol of 2,4-dihydroxy benzoate were fed intoa reaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was decreased from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour. In thepolyester block copolymer obtained, a melting point was 190° C., and anumber average molecular weight was 51000. The copolymer is designatedas Polyester block copolymer (P-D).

Preparation Example VII-5

[0584] 60 parts of a polybutylene terephthalate (A₁), 40 parts ofε-caprolactone, and 80% by mol of 2,4-dihydroxy benzoate were fed into areaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was decreased from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour. In thepolyester block copolymer obtained, a melting point was 200° C., and anumber average molecular weight was 63800. The copolymer is designatedas Polyester block copolymer (P-E).

Preparation Example VII-6

[0585] 60 parts of a polybutylene terephthalate (A₁) having a meltingpoint of 230° C., 40 parts of ε-caprolactone, and 0.5% by mol of2,4-dihydroxy benzoate were fed into a reaction vessel, and a reactionwas conducted at 235° C. for 1 hour while agitating.

[0586] Subsequently, pressure was decreased from an ordinary pressure tonot more than 1 torr over 1 hour while maintaining the temperature, andresidual ε-caprolactone in a system was removed while maintaining areduced pressure state for further 1 hour. In the polyester blockcopolymer obtained, a melting point was 204° C., and a number averagemolecular weight was 69100. The copolymer is designated as Polyesterblock copolymer (P-F).

Preparation Example VII-7

[0587] 60 parts of a polybutylene terephthalate (A₁) and 40 parts ofε-caprolactone were fed into a reaction vessel, and a reaction wasconducted at 235° C. for 1 hour while agitating. Subsequently, pressurewas decreased from an ordinary pressure to not more than 1 torr over 1hour while maintaining the temperature, and residual ε-caprolactone in asystem was removed while maintaining a reduced pressure state forfurther 1 hour. In the polyester block copolymer obtained, a meltingpoint was 204° C., and a number average molecular weight was 76500.

[0588] The copolymer is designated as Polyester block copolymer (P-G).

Preparation Example VII-8

[0589] 60 parts of a polybutylene terephthalate (A₁) having a meltingpoint of 230° C., 40 parts of ε-caprolactone, and 300% by mol of2,4-dihydroxy benzoate were fed into a reaction vessel, and a reactionwas conducted at 235° C. for 1 hour while agitating. Subsequently,pressure was reduced from an ordinary pressure to not more than 1 torrover 1 hour while maintaining the temperature, and residualε-caprolactone in a system was removed while maintaining a reducedpressure state for further 1 hour. In the polyester block copolymerobtained, a melting point was 179° C. which is fairly lowered. Asdescribed hereinabove, when a multifunctional compound is added in alarge amount, a melting point is largely lowered.

Examples VII-1 to VII-10

[0590] Polyester block copolymer composition is a mixture in whichcompounds selected from cyclohexane diglycidylester (CHDGE), KardularE10, sodium stearate, and Irganox 1010 are mixed with 100 parts byweight of the polyester block copolymers prepared in the PreparationExamples VII-1 to VII-6 in the weight part described in Table VII-1,respectively, and which is prepared by agitating at room temperature for30 minutes in a drum tumbler. The mixture was extruded using a 32 mmφtwin screw extruder at 230° C. for a heating time of period of 2.5minutes, and cut and pelletized after cooled in water.

[0591] Pellets obtained were fed into a tank type apparatus which can beheated and agitated, and can be pressure-reduced and purged by nitrogen,and preheated under conditions of 100° C. and 100 torr for 3 hours.Further, the apparatus was purged by nitrogen and returned to anordinary pressure, and a thermal treatment was conducted by elevating to180° C. After the treatment, it was cooled under a nitrogen atmosphereto take out pellets, and there were measured an MI value, a tensilestrength and extension, a melting point, color hue, an acid value, anumber average molecular weight, the modulus of strain hardening, and adraw-down property. Conditions for measurement and results are shown inTable VII-2.

[0592] As sown in the Tables VII-1 and VII-2, by the method of thepresent invention, there can be obtained resins having an excellentdraw-down property and color hue and, in which an acid value can bereduced by a small amount of the epoxy compounds, in which decline ofviscosity is less, and which have excellent physical properties.

[0593] Further, the mount of volatile components was less in melt-mixingcompared to the Comparative Examples as described hereinafter.

Comparative Examples VII-1 to VII-7

[0594] Polyester block copolymer composition is a mixture in whichcompounds selected from the CHDGE, Kardular E10, sodium stearate, andIrganox 1010 are mixed with the polyester block copolymers prepared inthe Preparation Examples VII-1 to VII-7 in the weight part described inTable VII-1, respectively, and which is prepared by agitating at roomtemperature for 30 minutes in a drum tumbler.

[0595] The mixture was extruded using a 32 mmφ twin screw extruder at atemperature and time of period adjusted as shown in Table VII-1 andwhile controlling an feeding amount, and cut and pelletized after cooledin water.

[0596] In relation to the pellets obtained, there were measured an MIvalue, a tensile strength and extension, a melting point, color hue, anacid value, a number average molecular weight, the modulus of strainhardening, and a draw-down property. Conditions for measurement andresults are shown in Table VII-2.

[0597] As shown in the Tables VII-1 and VII-2, it is confirmed thatalthough the draw-down property is partially observed, a level is small,and draw-down resistance is also small which is required in blowmolding. Further, it is confirmed that a large amount of epoxy compoundsare required in order to sufficiently lower an acid value, and therebecome worse physical properties such as color hue and viscosity.

Comparative Example VII-8

[0598] A composition was prepared by compounding using a twin screwextruder after formulating 30 parts by weight of Celloxide 2021 and 1part by weight of 2-phenylimidazole with the polyester block copolymerobtained in the Preparation Example VII-7. In relation to thecomposition obtained, there were measured an MI value, a tensilestrength and extension, a melting point, color hue, an acid value, anumber average molecular weight, the modulus of strain hardening, and adraw-down property. Conditions for measurement and results are shown inTable VII-2. The modulus of strain hardening was not observed.

Comparative Examples VII-9 to VII-11

[0599] Likewise as in the Examples VII-1 to VII-10, a polyester blockcopolymer composition is a mixture in which compounds selected from theCHDGE, Kardular E-10, sodium stearate, and Irganox 1010 are mixed with100 parts by weight of the polyester block copolymer prepared in thePreparation Example VII-7 in the weight part described in Table,respectively, which is prepared by agitating at room temperature for 30minutes in a drum tumbler. The mixture was extruded using a 32 mmφ twinscrew extruder at 230° C. and a heating time of period of 1 minute, andcut and pelletized after cooled in water.

[0600] Pellets obtained were fed into a tank type apparatus which can beheated and agitated and can be pressure-reduced and purged by nitrogen,and a thermal pretreatment was conducted at conditions of 100° C. and100 torr for 3 hours. Further, a thermal treatment was conducted at 180°C. after having returned to an ordinary pressure by purging nitrogen.After cooled under nitrogen, and pellets were taken out to measure an MIvalue, a tensile strength and extension, a melting point, color hue, anacid value, a number average molecular weight, a modulus of strainhardening, and a draw-down property. Conditions for measurement andresults are shown in Table VII-2. The modulus of strain hardening wasnot observed in all samples. TABLE VII-1 Poly- Melt ester Mixing MeltHeating Heat- block Kardula Sodium Irganox Temper- Mixing Temper- ingCopolymer CHDGE E10 Stearate 1010 ature Time ature Time Kind PBW PBW PBWPBW ° C. minute ° C. Hour C. Ex. VII-1 (A) 1.8 0.7 0.1 0.5 260 2.5 — —C. Ex. VII-2 (B) 1.8 0.7 0.1 0.5 260 2.5 — — C. Ex. VII-3 (C) 1.8 0.70.1 0.5 260 2.5 — — C. Ex. VII-4 (D) 1.8 0.7 0.1 0.5 260 2.5 — — C. Ex.VII-5 (E) 1.8 0.7 0.1 0.5 260 2.5 — — C. Ex. VII-6 (F) 1.8 0.7 0.1 0.5260 2.5 — — C. Ex. VII-7 (G) 1.8 0.7 0.1 0.5 260 2.5 — — C. Ex. VII-8(G) — — 0.1 0.5 260 2.5 — — C. Ex. VII-9 (G) 0.3 1.5 0.1 0.5 240 2.5 1808 C. Ex. VII-10 (G) 0.5 1.5 0.1 0.5 240 2.5 180 8 C. Ex. VII-11 (G) 0.71.5 0.1 0.5 240 2.5 180 8 Exam. VII-1 (A) 0.7 1.5 0.1 0.5 240 2.5 180 8Exam. VII-2 (B) 0.3 1.5 0.1 0.5 240 2.5 180 8 Exam. VII-3 (B) 0.5 1.50.1 0.5 240 2.5 180 8 Exam. VII-4 (B) 0.7 1.5 0.1 0.5 240 2.5 180 8Exam. VII-5 (C) 0.7 1.5 0.1 0.5 240 2.5 180 8 Exam. VII-6 (D) 0.7 1.50.1 0.5 240 2.5 180 8 Exam. VII-7 (E) 0.3 1.5 0.1 0.5 240 2.5 180 8Exam. VII-8 (E) 0.5 1.5 0.1 0.5 240 2.5 180 8 Exam. VII-9 (E) 0.7 1.50.1 0.5 240 2.5 180 8 Exam. VII-10 (F) 0.7 1.5 0.1 0.5 240 2.5 180 8

[0601] TABLE VII-2 MIV TSAB AV CH g/10 MP kg/ TEAB HR HTR NAMW mgKOH/g(YI) min ° C. cm² % % % MVS MSH DDP Mn C. Ex. VII-1 0.1 22 4.1 178 490700 100 100 1.2 0.6 2.0 65000 C. Ex. VII-2 0.1 22 4.8 188 450 710 100100 1.1 0.4 1.8 69500 C. Ex. VII-3 0.1 23 6.7 190 490 680 100 100 1.10.2 1.6 73300 C. Ex. VII-4 0.1 20 5.0 182 450 650 100 100 0.7 0.7 2.264000 C. Ex. VII-5 0.1 18 7.1 192 470 650 100 100 0.9 0.5 2.1 67800 C.Ex. VII-6 0.1 23 8.5 196 470 660 100 100 1.0 0.2 1.8 70100 C. Ex. VII-70.1 19 5.2 197 490 690 100 100 1.1 0 1.5 79000 C. Ex. VII-8 0.3 32 2.1188 480 700 70 80 0.7 0 3.5 73200 C. Ex. VII-9 0.1 16 1.7 203 440 680100 100 1.0 0 3.8 78500 C. Ex. VII-10 0.1 15 1.4 203 470 670 100 100 1.00 4.0 81000 C. Ex. VII-11 0.1 15 0.9 202 450 680 100 100 1.0 0 4.5 84400Exam. VII-1 0.1 16 0.8 189 490 700 100 100 1.0 1.4 4.6 69900 Exam. VII-20.1 16 1.9 198 490 660 100 100 1.0 0.5 3.5 67700 Exam. VII-3 0.1 14 1.6198 420 700 100 100 1.0 0.7 3.8 71000 Exam. VII-4 0.1 15 1.1 199 470 690100 100 1.0 0.9 4.2 74200 Exam. VII-5 0.1 15 0.9 204 460 710 100 100 1.00.5 4.3 76100 Exam. VII-6 0.1 17 0.8 190 480 640 100 100 0.9 1.6 4.472300 Exam. VII-7 0.1 18 2.2 200 450 690 100 100 0.9 0.6 3.2 65100 Exam.VII-8 0.1 18 1.5 201 480 690 100 100 0.9 1.0 3.9 67000 Exam. VII-9 0.119 0.8 201 480 700 100 100 0.9 1.2 4.4 77000 Exam. VII-10 0.1 16 0.9 205480 670 100 100 0.9 0.6 4.2 77100

[0602] By the present invention, there can be obtained a polyester blockcopolymer composition having an excellent moldability by which it can beapplied in blow molding and a variety of molding processes without anyhindrance, and which has an excellent heat resistance and rubberyelasticity.

1. A method for the preparation of a polyester block copolymer (P1)characterized in that in the method for the preparation of 100% byweight of the polyester block copolymer (P1) by allowing to react A% byweight of a crystalline aromatic polyester (A1) with B% by weight oflactones (B) (A+B=100), (B+0. 5)% by weight of lactones (B) areintroduced into A% by weight of a crystalline aromatic polyester (A1),and not less than 0.5% by weight of unreacted lactones are remained withrespect to 100% by weight of the polyester block copolymer (P1) afterpreparation of the copolymer.
 2. A method for the preparation of apolyester block copolymer (P1) as claimed in claim 1, wherein (B+2.5)%by weight of said lactones (B) are introduced and not less than 2.5% byweight of unreacted lactones are remained with respect to 100% by weightof said polyester block copolymer (P1) after preparation of thecopolymer.
 3. A method for the preparation of a polyester blockcopolymer (P1) as claimed in claim 1 or 2, wherein reaction proportion(A)/(B) of saidcrystalline aromatic polyester (A1) with respect to saidlactones (B) is 95/5-20/80.
 4. A method for the preparation of apolyester block copolymer (P1) as claimed in claims 1-3, wherein saidunreacted lactones are removed from said polyester block copolymer (P1).5. A method for the preparation of a polyester block copolymer (P1) asclaimed in any one of claims 1-4, wherein said unreacted lactones arecontinuously removed.
 6. A method for the preparation of a polyesterblock copolymer (P1) as claimed in any one of claims 1-5, wherein saidcrystalline aromatic polyester (A1) and said lactones (B) arecontinuously supplied into a reaction vessel and addition-polymerized,and said polyester block copolymer (P1) is continuously taken out.
 7. Amethod for the preparation of a polyester block copolymer (P1) asclaimed in any one of claims 1-6, wherein said crystalline aromaticpolyester (A1) is a polybutylene terephthalate.
 8. A method for thepreparation of a polyester block copolymer (P1) as claimed in any one ofclaims 1-7, wherein said lactones (B) are a caprolactone.
 9. A methodfor the preparation of a polyester block copolymer (P′1) having a highmolecular weight characterized in that a reaction is further conductedin a solid phase after having prepared said polyester block copolymer(P1) as claimed in any one of claims 1-8.
 10. A method for thepreparation of a polyester block copolymer (P′1) having a high molecularweight as claimed in claim 9, wherein said reaction in a solid phase iscontinuously conducted.
 11. A polyester block copolymer composition (R)obtained by thermally-processing a polyester block copolymer composition(Q) obtained by melt-mixing 100 parts by weight of a polyester blockcopolymer (P) with 0.1-5 parts by weight of an epoxy compound (C) havingone or more epoxy groups under an inert gas atmosphere and not less than120° C. in a solid phase, and further, at a temperature lower than amelting point of the polyester block copolymer composition (R) obtained.12. A polyester block copolymer composition (R) as claimed in claim 11,characterized in that said polyester block copolymer (P) is a polyesterblock copolymer (P1) obtained by allowing to react a crystallinearomatic polyester (A1) with lactones (B).
 13. A polyester blockcopolymer composition (R) as claimed in claim 11, characterized in thatthe polyester block copolymer (P) is a polyester block copolymer (P2)obtained by a polycondensation and/or ring-opening polymerization ofmonomer components constructing a crystalline polyester (A1); monomercomponents constructing a low crystalline polyester (A4); an aliphaticpolyether (A2); and/or polylactone (A3).
 14. A polyester block copolymercomposition (R) as claimed in any one of claims 11-13, characterized inthat said epoxy compound (C) is an epoxy compound (C2) having two ormore epoxy groups.
 15. A polyester block copolymer composition (R) asclaimed in any one of claims 11-14 which is obtained bythermally-processing said polyester block copolymer composition (Q) atnot less than 150° C. and, moreover, at a temperature of 100- to 5°C.-lower than a melting point of said polyester block copolymercomposition (R).
 16. A polyester block copolymer composition (R) asclaimed in any one of claims 11-15 which is obtained by furtherthermally-processing after preheating at a temperature lower than amelting point of the polyester block copolymer composition (R) and,moreover, at a temperature of not more than 150° C.
 17. A polyesterblock copolymer composition (R) as claimed in any one of claims 11-16,wherein there are mixed at least one kind of compounds selected from thegroup consisting of a hindered phenol-based compound, a sulphur-basedcompound, a phosphorus-based compound, a phenyl amine-based compound,and a hindered amine-based compound.
 18. A polyester block copolymercomposition (R) as claimed in any one of claims 11-17, wherein an acidvalue is not more than 0.5 mgKOH/g in said polyester block copolymercomposition (R) and, moreover, a melting point (Tm(R))) of saidcomposition (R) is 10° C.-lower than a melting point (Tm(P))) of saidpolyester block copolymer (P) which is a raw material. Tm (P)−10° ≦Tm(R)19. A polyester block copolymer composition (R) as claimed in any one ofclaims 11-18, wherein a melt viscosity stability (MI(T, P, t+10)/(MI(T,P, t)) is 0.5-2.0 in said polyester block copolymer composition (R), inthe formula, a melt index (MI(T, P, t)) value is a value measured at aheating temperature (T), loading (P), and heating time of period (t)based on a method described in Table 1 of JIS K7210, and herein, T is atemperature of 5° C.-higher than a melting point of said composition (R)and, it is a minimum temperature of experimental temperatures describedin Table 1 of the JIS K7210, and P is a value selected as ranging in1-30 g/10 minutes in an MI value, and the (MI(T, P, t)) is a value inwhich. the heating time of period is t+10 minutes in conditions of the Tand P.
 20. A method for the preparation of a polyester block copolymercomposition (R) characterized in that there is thermally-treated apolyester block copolymer composition (Q) in which 100 parts by weightof a polyester block copolymer (P) is thermally mixed with 0.1-5 partsby weight of an epoxy compound (C) having at least one epoxy groupsunder an inert gas atmosphere and at not less than 120° C. and atemperature less than a melting point of the obtained polyester blockcopolymer composition (R) in a solid phase.
 21. A polyester blockcopolymer composition which comprises thermally-kneading 100 parts byweight of a polyester block copolymer (P1) obtained by a reaction of acrystalline aromatic polyester (A1) with lactones (B) with 0.5-5.0 partsby weight of a mono or more functional epoxy compound (C) and 0.01-3.0parts by weight of a complex-formable agent for a metal (G).
 22. Apolyester block copolymer composition as claimed in claim 21, whereinsaid crystalline aromatic polyester (A1) is a polyester of an aromaticdicarboxylic acid which is an acid component (a) and an aliphaticdicarboxylic acid and/or a cycloaliphatic dicarboxylic acid which areoptionally added with an aliphatic diol, an aromatic diol, and/or acycloaliphatic diol which are a diol component (b).
 23. A polyesterblock copolymer composition as claimed in claim 21, wherein saidcrystalline aromatic polyester (A1) contains not less than 50% by weightof total of butylene terephthalate and ethylene terephthalate units. 24.A polyester block copolymer composition as claimed in any one of claims21-23, wherein a copolymerization proportion (A1/B) of said crystallinearomatic polyester (A1) with said lactones (B) is 97/3-50/50 by weight.25. A polyester block copolymer composition as claimed in any one ofclaims 21-24, wherein said epoxy compound (C) is a glycidyl type epoxycompound, a compound shown by any one of general formulae (I)-(V)described below, and a mixture thereof,

(in the formulae, R1, R2, R3 are an alkyl group and, at least one ofthose are a methyl group, and total carbon number thereof is 8 piecesand, further, “n” is 0-5.).
 26. A polyester block copolymer compositionas claimed in any one of claims 21-25, wherein said complex-formableagent for a metal (G) is at least one selected from the group consistingof an oxalic acid derivative, a salicylic acid derivative, and ahydrazide derivative.
 27. A heat-sensitive body for a heater cablecomposed of a polyester block copolymer composition as claimed in anyone of claims 21-26.
 28. A polyester block copolymer composition whichin obtaining said polyester block copolymer composition by allowing toreact said crystalline aromatic polyester (A1) with lactones (B),comprises adding 0.5-5.0 parts by weight of at least one kind of anepoxy compound (C) having one or more pieces of epoxy groups (includingat least 0.2 part by weight of two or more functional epoxy compound)and 0-2.0 parts by weight of a carbodiimide compound (E) to 100 parts byweight of a polyester block copolymer (P3) obtained by allowing to react0.1-100% by mol of at least one kind of a multifunctional compound (D)having at least three pieces of at least one of carboxylic group (i),hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with100% by mol of a crystalline aromatic polyester (A1), followed bythermally-kneading.
 29. A polyester block copolymer composition whichcomprises, in obtaining said polyester block copolymer composition byallowing to react the crystalline aromatic polyester (A1) with lactones(B), adding 0.1-5.0 parts by weight of at least one kind of an epoxycompound (C) having one or more pieces of epoxy groups and 0-2.0 partsby weight of a carbodiimide compound (E) to 100 parts by weight of apolyester block copolymer (P3) obtained by allowing to react 0.1-200% bymol of at least one kind of a multifunctional compound (D) having atleast three pieces of carboxylic group (i), hydroxyl group (ii), and/oran ester-formable group therefrom (iii) with 100% by mol of acrystalline aromatic polyester (A1), followed by thermally-kneading. [becommon in the present inventions V and VI]
 30. A polyester blockcopolymer composition as claimed in claim 28 or 29, wherein saidcrystalline aromatic polyester (A1) is a polyester of an aromaticdicarboxylic acid which is an essential acid component (a), an aliphaticdicarboxylic acid and/or a cycloaliphatic dicarboxylic acid which areoptionally added with an aliphatic diol, and an aromatic diol, and/or acycloaliphatic diol which are a diol component (b).
 31. A polyesterblock copolymer composition as claimed in any one of claims 28-30,wherein said crystalline aromatic polyester (A1) contains not less than50% by weight of total of butylene terephthalate and/or ethyleneterephthalate units.
 32. A polyester block copolymer composition asclaimed in any one of claims 28-30, wherein a copolymerizationproportion of said crystalline aromatic polyester (A1) with saidlactones (B) is the same proportion as described in claim
 24. 33. Apolyester block copolymer composition as claimed in any one of claims29-32, wherein at least one kind of said multifunctional compound (D)contains carboxylic group (i) or an ester-formable group therefrom. 34.A polyester block copolymer composition as claimed in any one of claims28-33, wherein said epoxy compound (C) is the same compound as describedin claim
 25. 35. A polyester block copolymer composition as claimed inany one of claims 28-34, which is employed for blow molding.
 36. Apolyester block copolymer composition (R) which comprises, in obtainingsaid polyester block copolymer composition by allowing to react thecrystalline aromatic polyester (A1) with lactones (B), heating apolyester block copolymer composition (Q) at a solid phase, and saidcomposition (Q) is obtained by formulating 0.1-5.0 parts by weight of atleast one kind of an epoxy compound (C) having one or more pieces ofepoxy groups with 100 parts by weight of a polyester block copolymer (P)obtained by allowing to react 0.1-200% by mol of at least one of amultifunctional compound (D) having at least three pieces of carboxylicgroup (i), hydroxyl group (ii), and/or an ester-formable group therefrom(iii) with 100% by mol of a crystalline aromatic polyester (A), followedby thermally-kneading.
 37. A polyester block copolymer composition (R)as claimed in claim 36, wherein at least one kind of saidmultifunctional compound (D) contains at least one of carboxylic group(i) or an ester-formable group therefrom.
 38. A polyester blockcopolymer composition (R) as claimed in claim 36 or 37, wherein saidepoxy compound (C) contains at least one kind of a bifunctional epoxycompound.
 39. A polyester block copolymer composition (R) as claimed inany one of claims 36-38, wherein said polyester block copolymercomposition (R) has an acid value of not more than 0.5 mgKOH/g and,moreover, a melting point Tm(R) is not less than 5° C.-lower than amelting point Tm(P) of said polyester block copolymer (P) before addingsaid epoxy compound, and Tm(R)≧Tm(P)−5° C.
 40. A polyester blockcopolymer composition as claimed in any one of claims 36-39, wherein amelt viscosity stability (MI-B)/(MI-A) is 0.5-2.0 which is calculatedfrom an MI value (MI-A) in said polyester block copolymer composition(R) and an MI value (MI-B) after heating for 10 minutes at a temperatureselected so as to be a lower temperature of the temperature described inJIS K7210.
 41. A polyester block copolymer composition as claimed in anyone of claims 36-40, which is a composition for blow molding. 42 Amethod for the preparation of a polyester block copolymer composition(R) characterized in that in obtaining the polyester block copolymercomposition by allowing to react said crystalline aromatic polyester (A)with lactones (B), there is heated a polyester block copolymercomposition (Q) at a solid phase, and said composition (Q) is obtainedby formulating 0.1-5.0 parts by weight of at least one kind of an epoxycompound (C) having one or more pieces of epoxy groups and 0-2.0 partsby weight of a carbodiimide compound (E) with 100 parts by weight of apolyester block copolymer (P) obtained by allowing to react 0.1-200% bymol of at least one kind of a multifunctional compound (D) having atleast three pieces of carboxylic group (i), hydroxyl group (ii), and/oran ester-formable group therefrom (iii) with 100% by mol of acrystalline aromatic polyester (A), followed by thermally-kneading. 43.A method for the preparation of a polyester block copolymer as claimedin claim 42, wherein heating is conducted in a solid phase at conditionsfrom a temperature lower than a melting point of said polyester blockcopolymer composition (R) to a temperature higher than a glasstransition temperature thereof in a solid phase under an inert gasatmosphere and, moreover, heating is conducted at a higher temperature(Ta) than 120° C., Tg<Ta<Tm (R), and 120° C.<Ta.
 44. A method for thepreparation of a polyester block copolymer as claimed in claim 42,wherein the temperature heating in a solid phase is 100- to 5C°-lowerthan a melting point of said polyester block copolymer composition (R)in a solid phase and, moreover, a temperature (Ta) higher than 150° C.,Tm(R)-100° C.≦Ta≦Tm(R)−5° C., and 150° C.≦Ta.
 45. A method for thepreparation of a polyester block copolymer as claimed in any one ofclaims 42-44, wherein heating is conducted in a solid phase atconditions of, (1) a temperature ranges from a temperature lower than amelting point of the polymer to a temperature higher than a glasstransition temperature of the polymer in a solid phase and, moreover,preheating is conducted at a temperature lower than 150° C. and atemperature (Tb) lower than Ta, and then, (2) a temperature ranges froma temperature lower than a melting point of the polymer to a temperaturehigher than a glass transition temperature of the polymer in a solidphase and, moreover, heating is conducted at a temperature higher than120° C., Preheating temperature Tb Tg<Tb<Tm(R), Tb<150° C., and Tb<TaHeating temperature Ta Tg<Ta<Tm(R), and 120° C.<Ta.